CA2135450A1 - Latex medium for a coating composition - Google Patents
Latex medium for a coating compositionInfo
- Publication number
- CA2135450A1 CA2135450A1 CA 2135450 CA2135450A CA2135450A1 CA 2135450 A1 CA2135450 A1 CA 2135450A1 CA 2135450 CA2135450 CA 2135450 CA 2135450 A CA2135450 A CA 2135450A CA 2135450 A1 CA2135450 A1 CA 2135450A1
- Authority
- CA
- Canada
- Prior art keywords
- latex
- parts
- medium
- weight
- particle size
- 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.)
- Abandoned
Links
- 229920000126 latex Polymers 0.000 title claims abstract description 61
- 239000004816 latex Substances 0.000 title claims abstract description 57
- 239000008199 coating composition Substances 0.000 title claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000003973 paint Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 239000002966 varnish Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011083 cement mortar Substances 0.000 claims 1
- 238000009988 textile finishing Methods 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000003999 initiator Substances 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 238000007792 addition Methods 0.000 description 11
- -1 vlnyl acetate Chemical class 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 9
- 239000000049 pigment Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000012875 nonionic emulsifier Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 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 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000004103 aminoalkyl group Chemical group 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001253 acrylic acids Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Polymers CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- UFHSKEHEWFGEFH-UHFFFAOYSA-N (2,5-dioxopyrrolidin-3-yl) prop-2-enoate Chemical compound C=CC(=O)OC1CC(=O)NC1=O UFHSKEHEWFGEFH-UHFFFAOYSA-N 0.000 description 1
- QKUGKZFASYQCGO-SREVYHEPSA-N (z)-4-oxo-4-phenylmethoxybut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1=CC=CC=C1 QKUGKZFASYQCGO-SREVYHEPSA-N 0.000 description 1
- ZWUBFMWIQJSEQS-UHFFFAOYSA-N 1,1-bis(ethenyl)cyclohexane Chemical compound C=CC1(C=C)CCCCC1 ZWUBFMWIQJSEQS-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- BHPDNFUVYQFFNK-UHFFFAOYSA-N 1-(hydroxymethyl)pyrrole-2,5-dione Chemical compound OCN1C(=O)C=CC1=O BHPDNFUVYQFFNK-UHFFFAOYSA-N 0.000 description 1
- DOGQRRGVLIGIEG-UHFFFAOYSA-N 1-(prop-2-enoylamino)butane-2-sulfonic acid Chemical compound CCC(S(O)(=O)=O)CNC(=O)C=C DOGQRRGVLIGIEG-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- FXUGUYXCZSDFLG-UHFFFAOYSA-N 2-(ditert-butylamino)ethyl prop-2-enoate Chemical compound CC(C)(C)N(C(C)(C)C)CCOC(=O)C=C FXUGUYXCZSDFLG-UHFFFAOYSA-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
- OTKLRHWBZHQJOP-UHFFFAOYSA-N 3-aminopropyl prop-2-enoate Chemical compound NCCCOC(=O)C=C OTKLRHWBZHQJOP-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-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
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Polymers CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 241001072332 Monia Species 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000429017 Pectis Species 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- VLSUKBCMGJXDLA-UHFFFAOYSA-N ethenesulfonic acid;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.OS(=O)(=O)C=C VLSUKBCMGJXDLA-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ZWGTVKDEOPDFGW-UHFFFAOYSA-N hexadecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[NH3+] ZWGTVKDEOPDFGW-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- HDCXQTPVTAIPNZ-UHFFFAOYSA-N n-({[4-(aminosulfonyl)phenyl]amino}carbonyl)-4-methylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC(=O)NC1=CC=C(S(N)(=O)=O)C=C1 HDCXQTPVTAIPNZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
- C08L1/284—Alkyl ethers with hydroxylated hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D157/00—Coating compositions based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
- C08L9/08—Latex
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paper (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
ABSTRACT
LATEX MEDIUM FOR A COATING COMPOSITION
The present invention relates to a medium for a coating composition based on film-forming latices prepared from unsaturated ethylenic monomers, characterized in that the said medium comprises, per 100 parts by weight of latex A (calculated on the basis of the solids content), which has a particle size of between 100 and 500 nm, from 0.1 to 100 parts by weight of latex B (calculated on the basis of the solids content) which has a particle size of between 5 and 40 nm.
Use of the above medium for the preparation of paper-coating compositions, varnishes and paints, adhesives, pressure-sensitive adhesives and the like.
LATEX MEDIUM FOR A COATING COMPOSITION
The present invention relates to a medium for a coating composition based on film-forming latices prepared from unsaturated ethylenic monomers, characterized in that the said medium comprises, per 100 parts by weight of latex A (calculated on the basis of the solids content), which has a particle size of between 100 and 500 nm, from 0.1 to 100 parts by weight of latex B (calculated on the basis of the solids content) which has a particle size of between 5 and 40 nm.
Use of the above medium for the preparation of paper-coating compositions, varnishes and paints, adhesives, pressure-sensitive adhesives and the like.
Description
~ 1 3 ~ 4 ~ O
LAT~ N3DI~N FOR A COATING COMæOSITION
The present invention relates to a latex medium for a coating composition.
Coating compositions based on a latex mediu~
are nowadays of a considerable technical and economic importance. Among these coating compositions particular mention may be made of papermaking compositions, that is to say for surface application for paper, and more particularly paper-coating co~positions, paint compositions, in particular varnish and paint compositions for the inside and for the outside, textile compositions, wood-coating compo~itions, adhesive compositions, pres~ure-sensitive adhesive (PSA) compositions, coating compositions for cement ~ ;
mortar, and the like.
Apart from the medium, these coating compositions co~prise at least one additional compo~ent chosen from a filler, a pigment, a surfactant, a thickening agent, an antioxidant, a natural binder ;`~
20 (starch, casein), a dispersing agent, an antifoam -agent, a biocide, and the like. ~ ~
One of the chief difficulties to be re~olved ~ -in developing them lies chiefly in that the compositions of the above type must have surface 25 properties which differ rrom the bulk properties. ~ -Thus, in the case where these compositions comprise ~ `
fillers and/or pigmsnts, the latex must adhesively bind the fillers together and to the ~ubstrate. -;
-' . -- ~'`;'`:`'~'`, ---` 2 1 3 ~ ~ ~ 0 ~ ~;
~ 73863-32 In addltlon, the latex partlcles must migrate to the surface of the coatlng in order that the coating should have a flne smooth appearance wlthollt asperitles, especlally wlth the alm of obtainlng good prlntablllty propertles. -Practlcal experlence shows that obtalnlng correct surface propertles runs counter to obtalnlng good bulk propertles.
The present lnventlon has made lt posslble to solve the above problem by proposlng a partlcular latex medlum maklng lt posslble to obtaln an entlrely advantageous compromlse between the bulk propertles and the surface propertles. ~;
In fact, accordlng to the lnventlon a medlum has been found for a coatlng composltlon based on fllm-formlng latlces prepared ~r from unsaturated ethylenlc monomers, characterized ln that the sald medlum comprlses, per 100 parts by welght of latex A
(calculated on the basls of the sollds content) whlch has a ~;
partlcle slze of between 100 and 500 mn, from 0.1 to 100 parts ~-by welght of latex B (calculated on the basls of the sollds , -..:
content)~ whlch has a partlcle slze of between 5 and 40 nm.
Latex A preferably has a partlcle slze of between 120 and 300 nm.
~,' In addltlon, preferably from 0.5 to 20 parts, or better stlll from 1 to 10 parts of latex B are employed per lO0 parts of latex A.
~ .
~` ~`'"'.
~' ~
h;~
`: ~
- 21354~o 3 73863-32 ;
Preparation of latex A~
The preparatlon of latex A ls descrlbed in many patent documents such as, for example, US 5,194,539 and EP 486,374. In addltlon, latlces A are avallable commerclally.
The polymerlzable monomers conælæt of at least one monomer chosen from styrene, butadlene, acryllc esters and vlnyl nltrlles.
Acryllc esters denote esters of acryllc acld and of methacryllc acld wlth Cl-C12, preferably Cl-C8 alkanolæ such aæ methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, -: : . : ...
lsobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, :~ -ethyl methacrylate, n-butyl methacrylate and lsobutyl i`; :- .;
methacrylate.
Vlnyl nltrlles lnclude those contalning from 3 to 12 carbon atoms, ln partlcular acrylonltrlle and methacrylonltrlle.
Styrene may be replaced entlrely or partlally wlth alpha-methylstyrene or vlnyltoluene.
Among the ethylenlcally unsaturated monomers capable ;-of be1ng polymerlzed wlth the above monomers, and the quantlty of whlch can range up to 40% by welght of the total of the monomers, there may be mentloned~
- carboxyllc acld vlnyl esters such as vlnyl acetate, vlnyl versatate, vlnyl proplDnate, =~
~c - ~ 2135~o 4 ~:
- ethylenic unsaturated mono- and dicarboxylic acids 6uch as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumarie acid and monoalkyl e6ter6 of dicarboxylic acid~ of the type referred to with alkanols which preferably contai~
1 to 4 carbon atoms and their N-substituted derivatives, - amides of unsaturated carboxylic acid~ ~uch as acrylamide, methacrylamide, N~
methalolacrylamide or -methacryl-~;de, - ethylenic monomers containing a sulphonic acid group and its alkali metal or a~monium salts, for example vinylsulphonic acid, -~
vinylbenzenesulphonic acid, alpha-acrylamidomethylpropanesulphonic acid and 2-sulphoethylene methacrylate, -- ethylenically unsaturated monomer6 containing a seaondary,.tertiary or quaternary amino group or a heterocyclic group containing nitrogen, for ;-~
example vinylpyridi3es, vinylimidazole, aminoalkyl : (meth)acrylates and amir.oalkyl (meth)acryla~ides uch as dimethylaminoethyl acrylate or methacrylate, di-tert-butylaminoethyl acrylate or -~ `
- methacrylate, dimethyla~ihomethylacrylamide or -methacrylamide etc., as well ao zwitterionic monomers such as sulphopropyl (dimethyl) ::~-:; e.i , .- . ~,.
aminopropyl acrylate etc., - esters of (meth)acrylic acids with .. , ~.'.' -~ 21354~o ~ :~
alkanediol~ preferably containing 2-8 carbon atoms, such as glycol mono(meth)acrylate, ~ .";;
hydroxypropyl mono(meth)acrylate, 1,4-butanediol `.
mono(meth)acrylate, and monomers containing two polymerizable double bonds, ~uch as ethylene ~-glycol dimethacrylate.
In addition to the abovementioned monomers it is also possible to use, in minor quantities which are also between 0.1 and 5 %, unsaturated ethylenic monomers of a crosslinkable nature, such as glycidyl (meth)acrylate or vinyl and acrylic silane~
3y way of example of compositions for the production of latex media there may be mentioned ~ `~
composition~ containing, on a weight basi~, 25-90 %, preferably 45-75 % of styrene and/or acrylonitrile, 75-10 %, preferably 55-25 %, of butadiene and/or acrylates, 0-20 %, preferably 1-10 % of unsaturated carboxylic acid and 0-40 %, preferably 0-15 %, of other unsaturated ethylenic monomers.
Polymerizat on is carried out in a manner ;~
known per se, in aqueous emulsion, of polymerizable ~-~
monomers in the pre~ence of at least one radical initiator and preferably in the presence of a transfer agent, for example of 'he mercaptan type, with a `'`~ J.
25 concentration of monomers in the reaction mixture which - ~
~ . . . ~.
is generally between 20 and 60 % by weight.
Any kind of free-radical initiator -con~entional in emulsion polymerization can be ~ ~ .
2135~0 suitable. !, Examples of initiators include hydroperoxides such as aqueous hydrogen peroxide, diisopropylbenzene hydroperoxide, Rodium, potassium or ammonium persulphates and cationic initiators such as azobisisobutyronitrile or 4,4'-azobis(4-cyanovaleric acid). ;~
These initiators may be used in combination -`
with a reducing agent such as, for example, bisulphite.
The quantity generally lies between 0.05 and 2 % by weight relative to the quantity of the monomer~.
The polymerization temperature, a function of the initiator used, is generally between 50C and 100C, preferably between 70 and 50C. The stabilization of the particlea is ensured, if need be, by any known colloidal sta~ilization system such as anionic, cationic, amphoteric and nonionic emulsifier~
Anionic emulsifiers are, for example, alkali metal alkyl sulphates, alkylsulphonates, ;~
alkylarylsulphonates and alkyl phosphates, dialkyl sulphosuccinates and sodium, potassium or ammonium salts of fatty acids, ~aturated or otherwise. Examples of cationic emul6ifiers are alkylpyridinium or alkylammonium salts such as N-ethyldodecyla~monium 25 chloride or bromide or cetylammonium chloride or `
bromide. Nonionic emulsi~iers which are mentioned in particular are polyoxyethylenated and/or polyoxypropylenated derivati~es of fatty alcohol~, of ..
., . . - ' ': ~ :~
213S4SO :
, fatty acids or of alkylphenols.
The polymerization may be carried out continuously, noncontinuously or semicontinuously with continuous introduction of a part of the monomers, and may be of the "seeded" or "incremental" type according to any known variant for obtaining particles of homogeneous and heterogeneous structure.
Preparation of latex B~
For convenience in the following description ;~ ;
it will be ~aid that latex B is made up of nanoparticles. Any monomer containing ethylenic ;~
unsaturation may be chosen as starting material and, in particular, the monomers and polymerization i~itiators ',i~'~ ,",~
referred to above in the case of latex A.
Among the polymers which may constitute the `
said latex 3 particles there may be mentioned ;-~
homopolymers or copolymers containing units derived from vinyl, acrylic and vinylaromatic monomers, from vinyl esters, from alkyl esters of a and unsaturated acids, from esters o8 unsaturated carboxylic acid~
from vinyl chloride, -rom vinylidene chloride and/or . ~ .
from dienes.
By way of illustration, the following monomers may be mentioned more particularly~
~ styrene and its derivatives (vinyltoluene, ethylvinylbenzene) - esters, hydroxyesters and amides of `
(meth)acrylic acid, such a~ methyl methacrylate, ;~
'~
213~4~0 ;~
butyl acrylate or (meth)acrylamide - vinyl esters ~vinyl acetate, vinyl ;
propionate) - vinyl and vinylidene chloride~
- vinylpyridines (2-vinylpyridine, 4 vi~ylpyridine, 2-methyl-5-vinylpyridine) - di(ethyl)aminoalkyl (meth)acrylates - ~ b ~-- di(ethyl)aminoalkyl(meth)acrylamides .
- allylamide - ethyleneimine -:
- ~meth)acrylonitrile - N-vinylimidazole - dialkylaminomethylstyrenes - vinylpyrrolidone - divinylbenzene and itC derivati~es - - conjugated dienes (butadiene etc.) - polyallyl derivatives (tetraallylethylene etc.) .~: .
- polyol (meth)acrylates (ethylene glycol dimethacrylate e~c.) - methylenebis(acryl2mide) :~
- bis(acrylamido)acetic acid.
By way OI vinyl and acryli-c monomers which are suitable for the invention there may be mentioned more particularly thoae derived from styrene, from acrylic acid, from acrylic ester of the type of N~
: hydroxysuccinimide acrylic ester~ such as N~
acryloyloxysuccinimide .~nd N-acryloyloxyphthal~mide~
,',~,."'.',',.
r ~35~o -~ -` - .
g ~
methacrylic acid, monobenzyl maleate, 2-vinylpyridine, Fityrene methylsulphonate, chloromethylstyrene, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, acrylonitrile and/or acrolein. ~-~
According to a variant, the particles have ion-forming or react ve groups at their surfaces, preferably chosen from OH, SO3H, SO3R, SO4R, COOH, CHO, PhCH2Cl, NH2, NR2, NR3 with R being a Cl-C3 alkyl radical, CONH2, NH-NH2, ;;
CN, CO2(CH2)~0H with n denoting an integer from 1 to 8, and N-hydroxyimide ester~
The functional groups present at the surface of the nanoparticles may also be derived from the ~ ~ -subsequent chemical conversion, for exa~ple by nucleophilic 6ubstitution, of one or a number of 15 reacti~e groups carried by the poly~er chain ~:
constituting the nanoparticles.
The nanoparticles according to the invention have a narrow particle size di6tribution. This monodi6persity of particle size makes it po6sible to have acce6s to the true adsorption surface of the nanoparticles and consequently to the optimum binding capacity for the latter, especially on fillers and pigments and on the substrate6 to be covered.
Any particle size distribution whose 6tandara 25 error is lower than or equal to 30 %, and preferably of ;~
the order of 20 %, is considered to be narrow.
The nanoparticles are capable of being obtained by polymerization of a direct microe~ulsion or `~ P
,~ ` `
-: , 213~o ,~
of the corresponding monomer~. The term microemulsion ~;
i8 intended to denote a thermodynamically stable dispersion in contrast to a di~persion which i8 only -;
kinetically stable and which coalesces at the end of a certain period.
The polymerization of a direct microemul ion ~-~
and the recovery of the said aqueous dispersion at the end of the polymerization are used, the said direct microemulsion being obtained beforehand by titration with the aid of an effective quantity o anionic surfactantt either of a direct emulsion stabilized with at least one ionic surfactant, or of an inverse . : :
emulsion stabilized with at least one nonionic surfactant, the two emulsions, called initial emulsions, consisting of at least one monomer in aqueous dispersion.
The aqueous dispersion of nanoparticles which is thus obtained may furthermore be subjected to a purification operation if appropriate.
In a first -t~ge, `herefore, the process involve~ the formation of this direct microemulsion.
In the case of an inverse initial emulsion the corresponding micrcemulsion i~ prepared by the 80- ~ -called inversion method inspired by the Schulman ~ ~
...... ~.. -.. ...
process (J.Phys.Chem. 1959, 63 p. 1677).
It consists, in a first step, in formulating - -~
an emulsion of the water-in-oil type, the oil --~
consisting of the monomer( 8) in question, with the aid ~ -- ..
- ~. ,...--:
LAT~ N3DI~N FOR A COATING COMæOSITION
The present invention relates to a latex medium for a coating composition.
Coating compositions based on a latex mediu~
are nowadays of a considerable technical and economic importance. Among these coating compositions particular mention may be made of papermaking compositions, that is to say for surface application for paper, and more particularly paper-coating co~positions, paint compositions, in particular varnish and paint compositions for the inside and for the outside, textile compositions, wood-coating compo~itions, adhesive compositions, pres~ure-sensitive adhesive (PSA) compositions, coating compositions for cement ~ ;
mortar, and the like.
Apart from the medium, these coating compositions co~prise at least one additional compo~ent chosen from a filler, a pigment, a surfactant, a thickening agent, an antioxidant, a natural binder ;`~
20 (starch, casein), a dispersing agent, an antifoam -agent, a biocide, and the like. ~ ~
One of the chief difficulties to be re~olved ~ -in developing them lies chiefly in that the compositions of the above type must have surface 25 properties which differ rrom the bulk properties. ~ -Thus, in the case where these compositions comprise ~ `
fillers and/or pigmsnts, the latex must adhesively bind the fillers together and to the ~ubstrate. -;
-' . -- ~'`;'`:`'~'`, ---` 2 1 3 ~ ~ ~ 0 ~ ~;
~ 73863-32 In addltlon, the latex partlcles must migrate to the surface of the coatlng in order that the coating should have a flne smooth appearance wlthollt asperitles, especlally wlth the alm of obtainlng good prlntablllty propertles. -Practlcal experlence shows that obtalnlng correct surface propertles runs counter to obtalnlng good bulk propertles.
The present lnventlon has made lt posslble to solve the above problem by proposlng a partlcular latex medlum maklng lt posslble to obtaln an entlrely advantageous compromlse between the bulk propertles and the surface propertles. ~;
In fact, accordlng to the lnventlon a medlum has been found for a coatlng composltlon based on fllm-formlng latlces prepared ~r from unsaturated ethylenlc monomers, characterized ln that the sald medlum comprlses, per 100 parts by welght of latex A
(calculated on the basls of the sollds content) whlch has a ~;
partlcle slze of between 100 and 500 mn, from 0.1 to 100 parts ~-by welght of latex B (calculated on the basls of the sollds , -..:
content)~ whlch has a partlcle slze of between 5 and 40 nm.
Latex A preferably has a partlcle slze of between 120 and 300 nm.
~,' In addltlon, preferably from 0.5 to 20 parts, or better stlll from 1 to 10 parts of latex B are employed per lO0 parts of latex A.
~ .
~` ~`'"'.
~' ~
h;~
`: ~
- 21354~o 3 73863-32 ;
Preparation of latex A~
The preparatlon of latex A ls descrlbed in many patent documents such as, for example, US 5,194,539 and EP 486,374. In addltlon, latlces A are avallable commerclally.
The polymerlzable monomers conælæt of at least one monomer chosen from styrene, butadlene, acryllc esters and vlnyl nltrlles.
Acryllc esters denote esters of acryllc acld and of methacryllc acld wlth Cl-C12, preferably Cl-C8 alkanolæ such aæ methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, -: : . : ...
lsobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, :~ -ethyl methacrylate, n-butyl methacrylate and lsobutyl i`; :- .;
methacrylate.
Vlnyl nltrlles lnclude those contalning from 3 to 12 carbon atoms, ln partlcular acrylonltrlle and methacrylonltrlle.
Styrene may be replaced entlrely or partlally wlth alpha-methylstyrene or vlnyltoluene.
Among the ethylenlcally unsaturated monomers capable ;-of be1ng polymerlzed wlth the above monomers, and the quantlty of whlch can range up to 40% by welght of the total of the monomers, there may be mentloned~
- carboxyllc acld vlnyl esters such as vlnyl acetate, vlnyl versatate, vlnyl proplDnate, =~
~c - ~ 2135~o 4 ~:
- ethylenic unsaturated mono- and dicarboxylic acids 6uch as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumarie acid and monoalkyl e6ter6 of dicarboxylic acid~ of the type referred to with alkanols which preferably contai~
1 to 4 carbon atoms and their N-substituted derivatives, - amides of unsaturated carboxylic acid~ ~uch as acrylamide, methacrylamide, N~
methalolacrylamide or -methacryl-~;de, - ethylenic monomers containing a sulphonic acid group and its alkali metal or a~monium salts, for example vinylsulphonic acid, -~
vinylbenzenesulphonic acid, alpha-acrylamidomethylpropanesulphonic acid and 2-sulphoethylene methacrylate, -- ethylenically unsaturated monomer6 containing a seaondary,.tertiary or quaternary amino group or a heterocyclic group containing nitrogen, for ;-~
example vinylpyridi3es, vinylimidazole, aminoalkyl : (meth)acrylates and amir.oalkyl (meth)acryla~ides uch as dimethylaminoethyl acrylate or methacrylate, di-tert-butylaminoethyl acrylate or -~ `
- methacrylate, dimethyla~ihomethylacrylamide or -methacrylamide etc., as well ao zwitterionic monomers such as sulphopropyl (dimethyl) ::~-:; e.i , .- . ~,.
aminopropyl acrylate etc., - esters of (meth)acrylic acids with .. , ~.'.' -~ 21354~o ~ :~
alkanediol~ preferably containing 2-8 carbon atoms, such as glycol mono(meth)acrylate, ~ .";;
hydroxypropyl mono(meth)acrylate, 1,4-butanediol `.
mono(meth)acrylate, and monomers containing two polymerizable double bonds, ~uch as ethylene ~-glycol dimethacrylate.
In addition to the abovementioned monomers it is also possible to use, in minor quantities which are also between 0.1 and 5 %, unsaturated ethylenic monomers of a crosslinkable nature, such as glycidyl (meth)acrylate or vinyl and acrylic silane~
3y way of example of compositions for the production of latex media there may be mentioned ~ `~
composition~ containing, on a weight basi~, 25-90 %, preferably 45-75 % of styrene and/or acrylonitrile, 75-10 %, preferably 55-25 %, of butadiene and/or acrylates, 0-20 %, preferably 1-10 % of unsaturated carboxylic acid and 0-40 %, preferably 0-15 %, of other unsaturated ethylenic monomers.
Polymerizat on is carried out in a manner ;~
known per se, in aqueous emulsion, of polymerizable ~-~
monomers in the pre~ence of at least one radical initiator and preferably in the presence of a transfer agent, for example of 'he mercaptan type, with a `'`~ J.
25 concentration of monomers in the reaction mixture which - ~
~ . . . ~.
is generally between 20 and 60 % by weight.
Any kind of free-radical initiator -con~entional in emulsion polymerization can be ~ ~ .
2135~0 suitable. !, Examples of initiators include hydroperoxides such as aqueous hydrogen peroxide, diisopropylbenzene hydroperoxide, Rodium, potassium or ammonium persulphates and cationic initiators such as azobisisobutyronitrile or 4,4'-azobis(4-cyanovaleric acid). ;~
These initiators may be used in combination -`
with a reducing agent such as, for example, bisulphite.
The quantity generally lies between 0.05 and 2 % by weight relative to the quantity of the monomer~.
The polymerization temperature, a function of the initiator used, is generally between 50C and 100C, preferably between 70 and 50C. The stabilization of the particlea is ensured, if need be, by any known colloidal sta~ilization system such as anionic, cationic, amphoteric and nonionic emulsifier~
Anionic emulsifiers are, for example, alkali metal alkyl sulphates, alkylsulphonates, ;~
alkylarylsulphonates and alkyl phosphates, dialkyl sulphosuccinates and sodium, potassium or ammonium salts of fatty acids, ~aturated or otherwise. Examples of cationic emul6ifiers are alkylpyridinium or alkylammonium salts such as N-ethyldodecyla~monium 25 chloride or bromide or cetylammonium chloride or `
bromide. Nonionic emulsi~iers which are mentioned in particular are polyoxyethylenated and/or polyoxypropylenated derivati~es of fatty alcohol~, of ..
., . . - ' ': ~ :~
213S4SO :
, fatty acids or of alkylphenols.
The polymerization may be carried out continuously, noncontinuously or semicontinuously with continuous introduction of a part of the monomers, and may be of the "seeded" or "incremental" type according to any known variant for obtaining particles of homogeneous and heterogeneous structure.
Preparation of latex B~
For convenience in the following description ;~ ;
it will be ~aid that latex B is made up of nanoparticles. Any monomer containing ethylenic ;~
unsaturation may be chosen as starting material and, in particular, the monomers and polymerization i~itiators ',i~'~ ,",~
referred to above in the case of latex A.
Among the polymers which may constitute the `
said latex 3 particles there may be mentioned ;-~
homopolymers or copolymers containing units derived from vinyl, acrylic and vinylaromatic monomers, from vinyl esters, from alkyl esters of a and unsaturated acids, from esters o8 unsaturated carboxylic acid~
from vinyl chloride, -rom vinylidene chloride and/or . ~ .
from dienes.
By way of illustration, the following monomers may be mentioned more particularly~
~ styrene and its derivatives (vinyltoluene, ethylvinylbenzene) - esters, hydroxyesters and amides of `
(meth)acrylic acid, such a~ methyl methacrylate, ;~
'~
213~4~0 ;~
butyl acrylate or (meth)acrylamide - vinyl esters ~vinyl acetate, vinyl ;
propionate) - vinyl and vinylidene chloride~
- vinylpyridines (2-vinylpyridine, 4 vi~ylpyridine, 2-methyl-5-vinylpyridine) - di(ethyl)aminoalkyl (meth)acrylates - ~ b ~-- di(ethyl)aminoalkyl(meth)acrylamides .
- allylamide - ethyleneimine -:
- ~meth)acrylonitrile - N-vinylimidazole - dialkylaminomethylstyrenes - vinylpyrrolidone - divinylbenzene and itC derivati~es - - conjugated dienes (butadiene etc.) - polyallyl derivatives (tetraallylethylene etc.) .~: .
- polyol (meth)acrylates (ethylene glycol dimethacrylate e~c.) - methylenebis(acryl2mide) :~
- bis(acrylamido)acetic acid.
By way OI vinyl and acryli-c monomers which are suitable for the invention there may be mentioned more particularly thoae derived from styrene, from acrylic acid, from acrylic ester of the type of N~
: hydroxysuccinimide acrylic ester~ such as N~
acryloyloxysuccinimide .~nd N-acryloyloxyphthal~mide~
,',~,."'.',',.
r ~35~o -~ -` - .
g ~
methacrylic acid, monobenzyl maleate, 2-vinylpyridine, Fityrene methylsulphonate, chloromethylstyrene, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxyethyl acrylate, acrylonitrile and/or acrolein. ~-~
According to a variant, the particles have ion-forming or react ve groups at their surfaces, preferably chosen from OH, SO3H, SO3R, SO4R, COOH, CHO, PhCH2Cl, NH2, NR2, NR3 with R being a Cl-C3 alkyl radical, CONH2, NH-NH2, ;;
CN, CO2(CH2)~0H with n denoting an integer from 1 to 8, and N-hydroxyimide ester~
The functional groups present at the surface of the nanoparticles may also be derived from the ~ ~ -subsequent chemical conversion, for exa~ple by nucleophilic 6ubstitution, of one or a number of 15 reacti~e groups carried by the poly~er chain ~:
constituting the nanoparticles.
The nanoparticles according to the invention have a narrow particle size di6tribution. This monodi6persity of particle size makes it po6sible to have acce6s to the true adsorption surface of the nanoparticles and consequently to the optimum binding capacity for the latter, especially on fillers and pigments and on the substrate6 to be covered.
Any particle size distribution whose 6tandara 25 error is lower than or equal to 30 %, and preferably of ;~
the order of 20 %, is considered to be narrow.
The nanoparticles are capable of being obtained by polymerization of a direct microe~ulsion or `~ P
,~ ` `
-: , 213~o ,~
of the corresponding monomer~. The term microemulsion ~;
i8 intended to denote a thermodynamically stable dispersion in contrast to a di~persion which i8 only -;
kinetically stable and which coalesces at the end of a certain period.
The polymerization of a direct microemul ion ~-~
and the recovery of the said aqueous dispersion at the end of the polymerization are used, the said direct microemulsion being obtained beforehand by titration with the aid of an effective quantity o anionic surfactantt either of a direct emulsion stabilized with at least one ionic surfactant, or of an inverse . : :
emulsion stabilized with at least one nonionic surfactant, the two emulsions, called initial emulsions, consisting of at least one monomer in aqueous dispersion.
The aqueous dispersion of nanoparticles which is thus obtained may furthermore be subjected to a purification operation if appropriate.
In a first -t~ge, `herefore, the process involve~ the formation of this direct microemulsion.
In the case of an inverse initial emulsion the corresponding micrcemulsion i~ prepared by the 80- ~ -called inversion method inspired by the Schulman ~ ~
...... ~.. -.. ...
process (J.Phys.Chem. 1959, 63 p. 1677).
It consists, in a first step, in formulating - -~
an emulsion of the water-in-oil type, the oil --~
consisting of the monomer( 8) in question, with the aid ~ -- ..
- ~. ,...--:
2~ 35 ~ ~ o 11 ~, .~, of a lipophilic nonionic emulsifier, that i8 to ~ay one with a low hydrophile-lipophile balance HLB. The oil forms approximately 70 % by wPight of the mixture. The quantity of this nonionic surfaetant i~ added 80 as to obtain a stabilized emulsion.
In general, a small quantity of an anionic surfactant is also added. Its ~uantity i6 appro~imately 0.5 % by weight relative to the weight of monomer. This emulsion i8 then inverted by addition of an aqueous solution of a hydrophilic nonicnic surfactant, that i8 to 6ay of high HLB until phase inversion is observed.
This phenomenon of inver6ion can be detected macroscopically, since during the titration a change is observed successively from a milky emulsion to a gel ~ ~;
and then to a transparent, staole, direct mieroemulsion of low ~iscosity.
The nonionic emulsifier used may be chosen from polyethoxylated nonylphenol (NP) derivatives. The lipophilic or hydrophilic nature of these co~pounds ~-20 varies as a fu~ction of the number of their ethoxy `;~
units. The pairs NP5/NPl 5, NPl 5/NPI 2, NP7/NPI 2 and NP7/NPI 5 may thus be mentioned as a pair of an ionie emulsifier of low HLB/nonionic emulsifier of high HLB.
According to a preferred embodiment the ~-inverse emulsion additionally and before its titration contains an anionic surfactant. This may be, for :`
exa~ple, sodium dodecylbenzene6ulphonate (DBS), ~odium 1auryl =u1phate (SDS~ or oodlu= dioetyl ~ulpho~eeirat-r~ ~ r~
2135~o :
(aerosol OT~
The nanoparticle dispersions obtained by this inverse emul~ion technique contain a large quantity of surfactants and cannot therefore be employed directly.
The removal of excess surfactants is obtained subsequently by using a purification technique. This removal i8 preferably carried out by dialysis which has -~
the advantage of not altering the particle size. No flocculation phenomenon is observed.
According to another process for the preparation of nanoparticles of latex ~, at least one of the monomers containing ethylenic unsaturation, referred to abo~e and capable of polymerizing in !~
aqueous emulsion, is added incrementally to the reactor and a polymerization initiator and at least one ~urfactant are added incrementally so that nanolatex 4~ ~ J
particles of particle size smaller than ~ nm are :: ..
obtained.
The term "incremental addition" includes all forms of addition of a small part of the monomer and/or of the initiator to the aqueous solution during a period of time necessary for all the monomer and all -the initiator to be added.
This includes cyclic addition~, noncontinuous 25 additions and their combinations. ~ ~
The addition of monomer and initiator is ` ~!"~'"`~' preferably continuous and kept constant during a certain period of time.
, . ' .. .''~
/~;
2135~o i ~ , The preferred monomers employed are alkyl acrylates and methacrylates in which the alkyl portio~
contain~ fro~ 1 to 10 carbon ato~s and carboxylic acids containing ethylenic un~aturation, such as acrylic, methacrylic, maleic, fumaric and itaconic acid and the corresponding amides.
In the caAe of copolymers derived partly from ;~
acrylic monomer~, a quantity of acrylic mono~er which is typically between 30 and 99 % of the total weight of the monomerA, preferably from 50 to 90 %, is employed.
For certain applications it i de irable that ~ ,:
the latex B should be crosslinked. To do this, a crosslinking agent is added to the reaction mixture for aqueous emulsion polymerization, which is chosen ~rom N-alkylol amides such as N-methylolacrylamide, N-methylolmaleimide, certain difunctional monomers such as divinylbenzne, divinylnaphthalene and divinylcyclohexane, as well as various diacrylates Ruch ;~
as ethylene glycol dimethacrylate.
, . ~. ~ .
The quantit e6 of crosslinking agents are generally between 0.05 and 10 %, from 0.1 to 5 % and `
preferably from 0.1 ~o 1.0 %, based on the total weight -of all the monomers added. '.. ".'.
As indicated above, any polymerization 25 initiator can be employed. ` -However, in the case where the initiator is water-soluble, which is the case with peroxides and , ~ ., .,,~i persulphates, it i6 critical to keep the ionicity o ~ . . .;~
'"' "'`"`' .. ..
.. .
. . .
213~4~0 the reaction mixture constant by removing a proportion of the water from the reaction mixture and by adding thi6 same water to the initiator feed stream.
It has been found, in fact, that by keeping a constant ionicity in the reaction mixture the agglomeration of the particles is avoided and particle~
exhibiting a narrower particle ~ize distribution are obtained. By diluting the water-soluble initiator with an appropriate quantity of water the ionic strength of the reacticn mixture is kept constant.
A semiconti~uous or continuous polymerization ;
proces~ may be employed for preparing latices B. This ~ r';!~
makes use of the addition, in an incremental manner, of the monomer, of the crosslinking agent if noed be and ~ fi of the lnitiator solution~ to the reactor, which is heated to a temperature which is generally between approximately 45 and 90C, water and at least one surfacta~t being ircluded during a certain period of ;-;~
time, in contrast to the noncontinuous ~'batch" process. `~
The reactor may optionally contain a small quantity of monomer before the beginning of the incremental polymerization, for the purpose of acting -as a "seed". Such a small quantity of monomer is generally lower than 30 % and preferably lower than ...-. .,,. - , .. . .
10 % of the total weight of the monomer employed.
The rate of addition of the monomer is generally governed by various factors such as the -;"
dimension~ of the reactor, the temperature increase due 2 1 3 5 4 ~ o to the exothermic reaction, the cooling capacity and the like, 80 that the reaction temperature i8 generally ~aintained in a specific range.
. . .:
The reaction mixture i8 maintained at a temperature between the ambient temperature (10 to 25C) and the boiling point of the aqueous golution.
~ -Y.'~
The reaction is generally performed at atmospheric pressure but it can be increased to promote the polymerization.
The monomer feed and the initiator feed must be combined as the ~ame single feed in the case where the initiator is ~oluble.
In addition, if the initiator is water~ -soluble and is an ionic salt such as ammonium 15 persulphate, this initiator is introduced into the ` ~-reactor so that the ionicity in the reaction mixture is maintained at a constant level. This objective is typically obtained by initially tran~ferring a proportion of the water .ro~ the reaction mixture to 20 the initiator feed in order to give ri~e to ion concentrations which are appreciably equal both in the feed and in the reactor. -Feeding the reactor using an incremental method generally makes it pos ible to obtain a a 2S stabilized concen~ration of free radicals, which ~akes it possible to avoid the low radical concentration~
observed during single initiator charges and prolonged `~
.-, .. . : ~
feed period~. It i~ the continuous availability of fre~
,,, 21354~0 ~ ~
~ .
16 73863-3~ ~
radicals that allows the formation of the new chaln and of the ~--particle to cornpete effectlvely with the addltion of monomer to already exlstlng particles, whlch results ln latex B particles ~-exhiblting an improved monodlspersity (that is to say a narrow partlcle slze distribution).
The terms "partlcle size dlstrlbutlon" or "partlcle slze" are lntended according to the invention to mean the ;
: . ~ ".
dlmenslon of the mean dlameter of the volume of the partlcle, . ~ . , .. ~ ..:
measured by photocorrelatlon spectroscopy. Latex B partlcles have a partlcle 9 ize which ls generally between 5 and 40 nm and :~
preferably between lO and 30 nm. ~.
Of course, the propertles of latex B depend to a large extent on the monomers chosen for their preparation. `
The constltuent monomers of latlces B may have a glass transltlon temperature Tg of between -54C and +130C. Of course, these Tg values rnust be chosen as a functlon of the type - i of chosen coatlng composltlons. A slmple rule, but not unl~ue ~ .:
ln the case of the medlum accordlng to the lnventlon, ls that, advantageously, the Tg of latex B is slmllar to the Tg of latex A. Thls rule can be applled ln particular to palnts.
When the medium accordlng to the lnventlon ls employed ;~^
ln papermaking compositlons, the latex A
. ~- ., ~
...... .
., .,~
;
.~
~135~
17 ~ -employed i8 generally a latex A of aa organic copolymer chosen from a styrene/butadiene, styrene/acrylate and styrene/butadiene/acrylate copolymer.
Pigment is added to the medium, such as, for exam~le, a mineral clay such as kaolin, calcium carbonate, titanium oxide, satin white, hydrargillite, talc, barium sulphate, plaster, as well as various adjuvants such as dispersing age~ts, natural binders such as starch, biocides, foa~ suppressor~, slip agents ~ ;
and the like.
A coating composition generally comprises: - ;
- 100 parts by weight of pigment, , ;
- 2 to 25 parts by weight o~ medium, `
- 1 to 10 parts by weight of adjuv~nts 8uch as those referred to above.
The medium content i8 lower (2 to 8 days) in :~
the case of compositions for photogravure (Rotogravure); it is greater (6 to 15 beams) in the `-case of offset compositions. ~ c The coating compositions according to the invention exhibit a better coating ratio, that is to say that, compared with Xnown compositions, the "`''.::.' '' ;'`'.'``?~
compositions according to the invention make it possible to obtain a satisfactory paper coating while employing less composition.
In addition, the medium according to the invention enables the fillers to be hidden better and - `
makes it possible to obtain a better ink uptake, which `~
o ,: , 18 ,:.
makes the papermaking compositions according to the invention more particularly advantageous for photogravure ("Rotogravure").
The compositions according to the invention .~
5 are also aimed at pressure-sensitive adhesive (PSA) .:-~ .,,.i.
compositions comprising a medium according to the invention. The compositions are traditionally based on an acrylic latex A such as, for example, tho~e described in patentfi US-A-5,164,441 and GB-A 1,257,940. .
~atex B is preferably hard with a Tg higher ..
than QC and prepared with the same monomers (generally `.-` , an alkyl (meth)acr,vlate and a (meth)acrylic acid). -~
In accordance with the inYention it has been found that the simultaneous addition of 0.01 to 0.3 % ~". ~:
15 by weight of a water-~oluble polymer such as .
carboxymethyl cellulose to latex B makes it possible to .. `~
obtain an asymmetric tack (adhesiveness) due to the rise of latex B to the surface at the time of drying. ";a~
In addition, the uGe of hard nanolatices B (Tg higher than or equal ~o 0) reduces "blocking" that i8 to say "tack", in other words the adhesiveness. ~ `
The present invention i8 also aimed more .
specifically at paint compositions comprising the : ~-., ~,.~
medium according to the invention in which the latices ,,,~., ";,., A and B are preferably essentially based on acrylic or styrene-acrylate copolymer based on at least one `~
alpha/beta un~aturated monoolefinic carboxylic monomer such as ~meth)acrylic acids and on at least one ~'-~. '..
,~ """,""',''.,, ~
2 ~L 3 ~ 4 5 o ~ :
19' (meth)acrylic acid e~ter of a pri~ary or secondary alcohol containing from 1 to 18 carbon atoms and optionally on styrene. Such latice~ A are, for example, de~cribed in US-A-3,320,198 and in EP-A 5,010,000 which are mentioned as reference.
In paints for the exterior it i8 reco~mended that latex A 6hould ha~e a Tg lower than 0C and that latex B should ha~e a Tg higher than 0C, preferably hisher than 10C.
In fact, in this particular case, the paint employed outside will exhibit a high resistance to soiling due to the migration of the particles of latex B to the surface.
To make an acrylic paint containing styrene/acrylate, the latex mediu~, preferably neutralized with a base (for example agueous a~monia or amine) i8 mixed in a known manner with a pigment dispersion containing usual adjuva~ts as well as pigments and pulverulent filler materials.
It has been found surprisingly and unexpectedly that the medium according to the invention permits wet abrasion resistance without affecting `~
stability.
In addition, as latex B tends to migrate to the external surface of the paint, the "hardness" of this surface can be modified by a suitable choice of the Tg of the constituent (co)polymer of latex B. ~ -In this paint application latex B prefarably -~
. ' 213~0 exhibits a Tg of between -50 and +50C, preferably between -30 and +30C.
The following exa~ples are given by way of ^ -illustration, no limitation whatever being implied.
In all that follows all that precedes, unleo~
the contrary is expressly mentioned, the parts and percentages are by weight. -EXAMP~E 1 Pre~aration of a latex A
The following monomers are introduced into a 25-litre reactor made of stainless steel, fitted with a stirrer and a jacket for circulating water enabling the temperature inside the reactor to be regulated at 80C
during the polymerization:
15 - 83 parts by weight of water, - 9 parts by weight of styrene, - 75.5 parts by weight of butyl acrylate, - 10 parts by weight of 2-ethylhexyl acrylate, ;
- 0.5 parts by weight of ethylene glycol dimethacrylate, - 2.7 parts by weight of acrylic acid, - 0.5 parts by weight of acrylamide, - 0.5 parts by weight of sodium sulphoethyl -~
methacrylate - 0.1 parts by weight of sodium alkylsulphonate, - 1.6 parts by weight of ammonium persulphate.
The polymerization is performed at 80C for ;~
~`','-'.''~
2~3~4~0 10 h.
The neutralized latex Lo has a mea~ particle size of 0.15 ~m, a Tg of -40C, a solids content of --~
53.3 %, a pH of 6 and a Brookfield viscosity, measured ~ `~
at 50 rev/min, of 280 mPa 8.
2-1 Preparation of a latex B~
In a 1-litre reactor made of stainlesE steel fitted with a stirrer and a jacket for circulating ; --- ~q;
10 water enabling the tempe`rature inside the reactor to be -regulated, a reaction stream consisting of the following is introduced into the reactor:
65 parts of butyl ac~ylate, ~ ~
25 parts of methacrylic acid, ~ æ"~".
10 parts of methyl methacrylate.
1 part of Vazo-64(3) (2,2'-azobisisobutyronitrile in solution in methyl methacrylate). :~
This feed solution is introduced in a ~-controlled manner into the reactor which contains 185 parts of water and 3 parts of sodium dodecyl sulphate.
The reactor is kept at 85C with constant stirring.
At the end of the addition of monomer the reactor is still kept at 85C for another hour. The reaction mixture is then taken to an almost complete conversion by treatment with 0.015 parts of t-butyl hydroperoxide and 0.015 parts of sodium metabisulphite at a temperature of 62C.
" """";''~
~' 21354~0 A latex with a solid~ co~tent of 25 % is ~ --obtained, with a particle size of 14 nm.
The latex is light in colour and has a Tg of approximately -5C.
2-2 Pre~aration of latex B (2) 0.15 parts of am~onium per~ulphate ~,'',. '~:,:!~"' predissolved ia 0.3 parts of water are added to a solution containing 2.57 parts of sodium lauryl sulphate a d 241 parts of water. After an initiation -~
period of 5 minutes a mixture of 43 partQ of butyl acrylate and 57 parts of butyl methacrylate i8 W`7-'~
introduced into the solution over 2 hours. The temperature i8 raised to 92C over 30 minutes and then the mixture is cooled and filtered.
A blue-grey latex is obtained which has a solid content of 23.10 %.
This latex has a particle ~ize smaller than 30 nm and a Tg of 0C.
2-3 Preparation of latex B (3) The operating method of example 2-2 is ;~
reproduced exactly except that 47 ~0 of methyl methacrylate, 43 % of butyl acrylate and 10 % of -methacrylic acid are employed.
This latex thus obtained has a particle size ~-smaller than 40 nm and a Tg of ~20C.
2-4 Preparation o$ latex B (4) -,-~: . :: .
The operating method of example 2-2 is reproduced exactly except that 20 % of methyl ;-.. ""' ~'.
, ~
methacrylate, 70 % of butyl acrylate and 10 % of -~ "
methacrylic acid are e~ployed. This latex thus obtainod .;
ha6 a particle size smaller tha~ 40 nm and a Tg of -20C.
EXAMPLE 3:
Pre~aration of the media The media Ll, L2, L3 and L~ are prepared Qimply by mixing, at slightly acidic pH, 100 parts of latex A
and 10 parts of lati~es B~l), B(2), B(3) and B(4) `~
10 respecti~ely. The media Ll, L2, L3 and L~ thu~ obtained .`~
ha~e solid~ contents of approximately 50 %.
Preparation of the ~aint:
The pigment pa6te which ha~ the following composition (in parts by weight) is prepared simply by .
15 mixing in a paint disperser:
Water 3000 - ~.
Tylose MH 6000 XP ~ (thickener)40 Coatex P 50 ~g (acrylic dispersant) 37 ;;
Clérol TPE 714 ~ (antifoam) 20 :~
Proxel BD ~ (biocide) 9 ..
TiO2 RL68 530 Omyalite 90 (calcium carbonate of particle size ~ l~m) 2130 D~rcol 50 (calcium carbonate of particle size smaller than 5 ~m)3200 to 89.66 parts of this pigment paste are added 15 part~
of a modium chosen from ~2~ L3 and L~ and 0.9 parts of water, to obtain a paint P2, P3 and P~, re~pecti~ely, : .- , ~-~ .
- . ~: :;
: ~` :`:
~ 1 3 5 4 5 0 ~ ~
i ., , ~ ~
which has a Pigment Volume Concentration (PVC) of approximately 75 %. - ~`
Characteristics of the media L" L3, L, and of the ~aint8 P2~ P3~ P~
The following are determined on the media L
L3 and L, and the paints P2, P, and P,: ;
- Brookfield viscosity at 50 rev/min (v) - storage stability 28 days at 55C.
To do thi~, a sample of medium or o~ paint i8 `,`:. ,~ ; `
10 heated at 55C for 28 days in a receptacle protected `-from air. The stability (S) of the medium or of the -paint is given by the ratio of the Brookfield viscositieE of the paints, measured at 50 rev/min at 20~ after 30 day~, to the initial visco~ity.
Also measured on the media L2, L3 a d L~ are~
the pH, the solid~ content (%) and the minimum fil~
forming temperature (MFFT in C), that is to say the lowest temperature at which a film is obtained. A wet abrasion resistance (WAR) test is performed on the `~
20 paints P2, P3 and P~, which i~ performed with the aid o~ ;
a C-- abrasiometer according to DIN Standard 53778. ~he WAR is evaluated as the number of cycles at the end of which the paint i8 eroded.
The results obtained are collated in Table 1 below insofar as the media are concerned and in Table 2 below in~ofar a~ the paints are concerned.
'' ', :' ' ''`""
`' ,`'`'',''`.",`'~``'`
`;~
, ' ' '~
` 2 1 3 5 ~ ~ o TABLE 1 .
- ., .;,..........
~-di~= ~ pH SC ~ (=P- ~) 5 Z8 d/ MFFT
._ ,',, ` ',- ~.'`~
L? 7.7 47.9 2080 0.75 0 ; ` ~
.~ ,, _ _ - ___ -', ,. . ' ` ,' -.-.'-.
L3 8 47.8 1200 0.65 0 , . .__ Ls 7.8 48.0 600 1.05 0 , ....... . ,__ ' `,~
,__ "'~
Paint Medi~ V S 28 d/ WAR (~o.
.___. employed (mPa 8)55C of cyrle~) Pl L2 4080 1 3910 ._ p3 L3 4440 1.15 1370 .
_ .~
P~ L~ 4120 1.1 3400 , __ _ ,,_, ,~,__ ~ .. ,.. ,,.,,,,", Po LA 3560 1.05 2550 Paint Po i8 a control paint prepared only with the medium LA.
From Tables 1 and 2 above it appears that paints which have satis$actory viscosities and which remain perfectly stable at the end of the 28 days at 55C are obtained. ~:
It is noted, furthermore, that the addition of binder B with Tg = 0C greatly improves the WAR.
~ ' : ~! . , . ~ .!
In general, a small quantity of an anionic surfactant is also added. Its ~uantity i6 appro~imately 0.5 % by weight relative to the weight of monomer. This emulsion i8 then inverted by addition of an aqueous solution of a hydrophilic nonicnic surfactant, that i8 to 6ay of high HLB until phase inversion is observed.
This phenomenon of inver6ion can be detected macroscopically, since during the titration a change is observed successively from a milky emulsion to a gel ~ ~;
and then to a transparent, staole, direct mieroemulsion of low ~iscosity.
The nonionic emulsifier used may be chosen from polyethoxylated nonylphenol (NP) derivatives. The lipophilic or hydrophilic nature of these co~pounds ~-20 varies as a fu~ction of the number of their ethoxy `;~
units. The pairs NP5/NPl 5, NPl 5/NPI 2, NP7/NPI 2 and NP7/NPI 5 may thus be mentioned as a pair of an ionie emulsifier of low HLB/nonionic emulsifier of high HLB.
According to a preferred embodiment the ~-inverse emulsion additionally and before its titration contains an anionic surfactant. This may be, for :`
exa~ple, sodium dodecylbenzene6ulphonate (DBS), ~odium 1auryl =u1phate (SDS~ or oodlu= dioetyl ~ulpho~eeirat-r~ ~ r~
2135~o :
(aerosol OT~
The nanoparticle dispersions obtained by this inverse emul~ion technique contain a large quantity of surfactants and cannot therefore be employed directly.
The removal of excess surfactants is obtained subsequently by using a purification technique. This removal i8 preferably carried out by dialysis which has -~
the advantage of not altering the particle size. No flocculation phenomenon is observed.
According to another process for the preparation of nanoparticles of latex ~, at least one of the monomers containing ethylenic unsaturation, referred to abo~e and capable of polymerizing in !~
aqueous emulsion, is added incrementally to the reactor and a polymerization initiator and at least one ~urfactant are added incrementally so that nanolatex 4~ ~ J
particles of particle size smaller than ~ nm are :: ..
obtained.
The term "incremental addition" includes all forms of addition of a small part of the monomer and/or of the initiator to the aqueous solution during a period of time necessary for all the monomer and all -the initiator to be added.
This includes cyclic addition~, noncontinuous 25 additions and their combinations. ~ ~
The addition of monomer and initiator is ` ~!"~'"`~' preferably continuous and kept constant during a certain period of time.
, . ' .. .''~
/~;
2135~o i ~ , The preferred monomers employed are alkyl acrylates and methacrylates in which the alkyl portio~
contain~ fro~ 1 to 10 carbon ato~s and carboxylic acids containing ethylenic un~aturation, such as acrylic, methacrylic, maleic, fumaric and itaconic acid and the corresponding amides.
In the caAe of copolymers derived partly from ;~
acrylic monomer~, a quantity of acrylic mono~er which is typically between 30 and 99 % of the total weight of the monomerA, preferably from 50 to 90 %, is employed.
For certain applications it i de irable that ~ ,:
the latex B should be crosslinked. To do this, a crosslinking agent is added to the reaction mixture for aqueous emulsion polymerization, which is chosen ~rom N-alkylol amides such as N-methylolacrylamide, N-methylolmaleimide, certain difunctional monomers such as divinylbenzne, divinylnaphthalene and divinylcyclohexane, as well as various diacrylates Ruch ;~
as ethylene glycol dimethacrylate.
, . ~. ~ .
The quantit e6 of crosslinking agents are generally between 0.05 and 10 %, from 0.1 to 5 % and `
preferably from 0.1 ~o 1.0 %, based on the total weight -of all the monomers added. '.. ".'.
As indicated above, any polymerization 25 initiator can be employed. ` -However, in the case where the initiator is water-soluble, which is the case with peroxides and , ~ ., .,,~i persulphates, it i6 critical to keep the ionicity o ~ . . .;~
'"' "'`"`' .. ..
.. .
. . .
213~4~0 the reaction mixture constant by removing a proportion of the water from the reaction mixture and by adding thi6 same water to the initiator feed stream.
It has been found, in fact, that by keeping a constant ionicity in the reaction mixture the agglomeration of the particles is avoided and particle~
exhibiting a narrower particle ~ize distribution are obtained. By diluting the water-soluble initiator with an appropriate quantity of water the ionic strength of the reacticn mixture is kept constant.
A semiconti~uous or continuous polymerization ;
proces~ may be employed for preparing latices B. This ~ r';!~
makes use of the addition, in an incremental manner, of the monomer, of the crosslinking agent if noed be and ~ fi of the lnitiator solution~ to the reactor, which is heated to a temperature which is generally between approximately 45 and 90C, water and at least one surfacta~t being ircluded during a certain period of ;-;~
time, in contrast to the noncontinuous ~'batch" process. `~
The reactor may optionally contain a small quantity of monomer before the beginning of the incremental polymerization, for the purpose of acting -as a "seed". Such a small quantity of monomer is generally lower than 30 % and preferably lower than ...-. .,,. - , .. . .
10 % of the total weight of the monomer employed.
The rate of addition of the monomer is generally governed by various factors such as the -;"
dimension~ of the reactor, the temperature increase due 2 1 3 5 4 ~ o to the exothermic reaction, the cooling capacity and the like, 80 that the reaction temperature i8 generally ~aintained in a specific range.
. . .:
The reaction mixture i8 maintained at a temperature between the ambient temperature (10 to 25C) and the boiling point of the aqueous golution.
~ -Y.'~
The reaction is generally performed at atmospheric pressure but it can be increased to promote the polymerization.
The monomer feed and the initiator feed must be combined as the ~ame single feed in the case where the initiator is ~oluble.
In addition, if the initiator is water~ -soluble and is an ionic salt such as ammonium 15 persulphate, this initiator is introduced into the ` ~-reactor so that the ionicity in the reaction mixture is maintained at a constant level. This objective is typically obtained by initially tran~ferring a proportion of the water .ro~ the reaction mixture to 20 the initiator feed in order to give ri~e to ion concentrations which are appreciably equal both in the feed and in the reactor. -Feeding the reactor using an incremental method generally makes it pos ible to obtain a a 2S stabilized concen~ration of free radicals, which ~akes it possible to avoid the low radical concentration~
observed during single initiator charges and prolonged `~
.-, .. . : ~
feed period~. It i~ the continuous availability of fre~
,,, 21354~0 ~ ~
~ .
16 73863-3~ ~
radicals that allows the formation of the new chaln and of the ~--particle to cornpete effectlvely with the addltion of monomer to already exlstlng particles, whlch results ln latex B particles ~-exhiblting an improved monodlspersity (that is to say a narrow partlcle slze distribution).
The terms "partlcle size dlstrlbutlon" or "partlcle slze" are lntended according to the invention to mean the ;
: . ~ ".
dlmenslon of the mean dlameter of the volume of the partlcle, . ~ . , .. ~ ..:
measured by photocorrelatlon spectroscopy. Latex B partlcles have a partlcle 9 ize which ls generally between 5 and 40 nm and :~
preferably between lO and 30 nm. ~.
Of course, the propertles of latex B depend to a large extent on the monomers chosen for their preparation. `
The constltuent monomers of latlces B may have a glass transltlon temperature Tg of between -54C and +130C. Of course, these Tg values rnust be chosen as a functlon of the type - i of chosen coatlng composltlons. A slmple rule, but not unl~ue ~ .:
ln the case of the medlum accordlng to the lnventlon, ls that, advantageously, the Tg of latex B is slmllar to the Tg of latex A. Thls rule can be applled ln particular to palnts.
When the medium accordlng to the lnventlon ls employed ;~^
ln papermaking compositlons, the latex A
. ~- ., ~
...... .
., .,~
;
.~
~135~
17 ~ -employed i8 generally a latex A of aa organic copolymer chosen from a styrene/butadiene, styrene/acrylate and styrene/butadiene/acrylate copolymer.
Pigment is added to the medium, such as, for exam~le, a mineral clay such as kaolin, calcium carbonate, titanium oxide, satin white, hydrargillite, talc, barium sulphate, plaster, as well as various adjuvants such as dispersing age~ts, natural binders such as starch, biocides, foa~ suppressor~, slip agents ~ ;
and the like.
A coating composition generally comprises: - ;
- 100 parts by weight of pigment, , ;
- 2 to 25 parts by weight o~ medium, `
- 1 to 10 parts by weight of adjuv~nts 8uch as those referred to above.
The medium content i8 lower (2 to 8 days) in :~
the case of compositions for photogravure (Rotogravure); it is greater (6 to 15 beams) in the `-case of offset compositions. ~ c The coating compositions according to the invention exhibit a better coating ratio, that is to say that, compared with Xnown compositions, the "`''.::.' '' ;'`'.'``?~
compositions according to the invention make it possible to obtain a satisfactory paper coating while employing less composition.
In addition, the medium according to the invention enables the fillers to be hidden better and - `
makes it possible to obtain a better ink uptake, which `~
o ,: , 18 ,:.
makes the papermaking compositions according to the invention more particularly advantageous for photogravure ("Rotogravure").
The compositions according to the invention .~
5 are also aimed at pressure-sensitive adhesive (PSA) .:-~ .,,.i.
compositions comprising a medium according to the invention. The compositions are traditionally based on an acrylic latex A such as, for example, tho~e described in patentfi US-A-5,164,441 and GB-A 1,257,940. .
~atex B is preferably hard with a Tg higher ..
than QC and prepared with the same monomers (generally `.-` , an alkyl (meth)acr,vlate and a (meth)acrylic acid). -~
In accordance with the inYention it has been found that the simultaneous addition of 0.01 to 0.3 % ~". ~:
15 by weight of a water-~oluble polymer such as .
carboxymethyl cellulose to latex B makes it possible to .. `~
obtain an asymmetric tack (adhesiveness) due to the rise of latex B to the surface at the time of drying. ";a~
In addition, the uGe of hard nanolatices B (Tg higher than or equal ~o 0) reduces "blocking" that i8 to say "tack", in other words the adhesiveness. ~ `
The present invention i8 also aimed more .
specifically at paint compositions comprising the : ~-., ~,.~
medium according to the invention in which the latices ,,,~., ";,., A and B are preferably essentially based on acrylic or styrene-acrylate copolymer based on at least one `~
alpha/beta un~aturated monoolefinic carboxylic monomer such as ~meth)acrylic acids and on at least one ~'-~. '..
,~ """,""',''.,, ~
2 ~L 3 ~ 4 5 o ~ :
19' (meth)acrylic acid e~ter of a pri~ary or secondary alcohol containing from 1 to 18 carbon atoms and optionally on styrene. Such latice~ A are, for example, de~cribed in US-A-3,320,198 and in EP-A 5,010,000 which are mentioned as reference.
In paints for the exterior it i8 reco~mended that latex A 6hould ha~e a Tg lower than 0C and that latex B should ha~e a Tg higher than 0C, preferably hisher than 10C.
In fact, in this particular case, the paint employed outside will exhibit a high resistance to soiling due to the migration of the particles of latex B to the surface.
To make an acrylic paint containing styrene/acrylate, the latex mediu~, preferably neutralized with a base (for example agueous a~monia or amine) i8 mixed in a known manner with a pigment dispersion containing usual adjuva~ts as well as pigments and pulverulent filler materials.
It has been found surprisingly and unexpectedly that the medium according to the invention permits wet abrasion resistance without affecting `~
stability.
In addition, as latex B tends to migrate to the external surface of the paint, the "hardness" of this surface can be modified by a suitable choice of the Tg of the constituent (co)polymer of latex B. ~ -In this paint application latex B prefarably -~
. ' 213~0 exhibits a Tg of between -50 and +50C, preferably between -30 and +30C.
The following exa~ples are given by way of ^ -illustration, no limitation whatever being implied.
In all that follows all that precedes, unleo~
the contrary is expressly mentioned, the parts and percentages are by weight. -EXAMP~E 1 Pre~aration of a latex A
The following monomers are introduced into a 25-litre reactor made of stainless steel, fitted with a stirrer and a jacket for circulating water enabling the temperature inside the reactor to be regulated at 80C
during the polymerization:
15 - 83 parts by weight of water, - 9 parts by weight of styrene, - 75.5 parts by weight of butyl acrylate, - 10 parts by weight of 2-ethylhexyl acrylate, ;
- 0.5 parts by weight of ethylene glycol dimethacrylate, - 2.7 parts by weight of acrylic acid, - 0.5 parts by weight of acrylamide, - 0.5 parts by weight of sodium sulphoethyl -~
methacrylate - 0.1 parts by weight of sodium alkylsulphonate, - 1.6 parts by weight of ammonium persulphate.
The polymerization is performed at 80C for ;~
~`','-'.''~
2~3~4~0 10 h.
The neutralized latex Lo has a mea~ particle size of 0.15 ~m, a Tg of -40C, a solids content of --~
53.3 %, a pH of 6 and a Brookfield viscosity, measured ~ `~
at 50 rev/min, of 280 mPa 8.
2-1 Preparation of a latex B~
In a 1-litre reactor made of stainlesE steel fitted with a stirrer and a jacket for circulating ; --- ~q;
10 water enabling the tempe`rature inside the reactor to be -regulated, a reaction stream consisting of the following is introduced into the reactor:
65 parts of butyl ac~ylate, ~ ~
25 parts of methacrylic acid, ~ æ"~".
10 parts of methyl methacrylate.
1 part of Vazo-64(3) (2,2'-azobisisobutyronitrile in solution in methyl methacrylate). :~
This feed solution is introduced in a ~-controlled manner into the reactor which contains 185 parts of water and 3 parts of sodium dodecyl sulphate.
The reactor is kept at 85C with constant stirring.
At the end of the addition of monomer the reactor is still kept at 85C for another hour. The reaction mixture is then taken to an almost complete conversion by treatment with 0.015 parts of t-butyl hydroperoxide and 0.015 parts of sodium metabisulphite at a temperature of 62C.
" """";''~
~' 21354~0 A latex with a solid~ co~tent of 25 % is ~ --obtained, with a particle size of 14 nm.
The latex is light in colour and has a Tg of approximately -5C.
2-2 Pre~aration of latex B (2) 0.15 parts of am~onium per~ulphate ~,'',. '~:,:!~"' predissolved ia 0.3 parts of water are added to a solution containing 2.57 parts of sodium lauryl sulphate a d 241 parts of water. After an initiation -~
period of 5 minutes a mixture of 43 partQ of butyl acrylate and 57 parts of butyl methacrylate i8 W`7-'~
introduced into the solution over 2 hours. The temperature i8 raised to 92C over 30 minutes and then the mixture is cooled and filtered.
A blue-grey latex is obtained which has a solid content of 23.10 %.
This latex has a particle ~ize smaller than 30 nm and a Tg of 0C.
2-3 Preparation of latex B (3) The operating method of example 2-2 is ;~
reproduced exactly except that 47 ~0 of methyl methacrylate, 43 % of butyl acrylate and 10 % of -methacrylic acid are employed.
This latex thus obtained has a particle size ~-smaller than 40 nm and a Tg of ~20C.
2-4 Preparation o$ latex B (4) -,-~: . :: .
The operating method of example 2-2 is reproduced exactly except that 20 % of methyl ;-.. ""' ~'.
, ~
methacrylate, 70 % of butyl acrylate and 10 % of -~ "
methacrylic acid are e~ployed. This latex thus obtainod .;
ha6 a particle size smaller tha~ 40 nm and a Tg of -20C.
EXAMPLE 3:
Pre~aration of the media The media Ll, L2, L3 and L~ are prepared Qimply by mixing, at slightly acidic pH, 100 parts of latex A
and 10 parts of lati~es B~l), B(2), B(3) and B(4) `~
10 respecti~ely. The media Ll, L2, L3 and L~ thu~ obtained .`~
ha~e solid~ contents of approximately 50 %.
Preparation of the ~aint:
The pigment pa6te which ha~ the following composition (in parts by weight) is prepared simply by .
15 mixing in a paint disperser:
Water 3000 - ~.
Tylose MH 6000 XP ~ (thickener)40 Coatex P 50 ~g (acrylic dispersant) 37 ;;
Clérol TPE 714 ~ (antifoam) 20 :~
Proxel BD ~ (biocide) 9 ..
TiO2 RL68 530 Omyalite 90 (calcium carbonate of particle size ~ l~m) 2130 D~rcol 50 (calcium carbonate of particle size smaller than 5 ~m)3200 to 89.66 parts of this pigment paste are added 15 part~
of a modium chosen from ~2~ L3 and L~ and 0.9 parts of water, to obtain a paint P2, P3 and P~, re~pecti~ely, : .- , ~-~ .
- . ~: :;
: ~` :`:
~ 1 3 5 4 5 0 ~ ~
i ., , ~ ~
which has a Pigment Volume Concentration (PVC) of approximately 75 %. - ~`
Characteristics of the media L" L3, L, and of the ~aint8 P2~ P3~ P~
The following are determined on the media L
L3 and L, and the paints P2, P, and P,: ;
- Brookfield viscosity at 50 rev/min (v) - storage stability 28 days at 55C.
To do thi~, a sample of medium or o~ paint i8 `,`:. ,~ ; `
10 heated at 55C for 28 days in a receptacle protected `-from air. The stability (S) of the medium or of the -paint is given by the ratio of the Brookfield viscositieE of the paints, measured at 50 rev/min at 20~ after 30 day~, to the initial visco~ity.
Also measured on the media L2, L3 a d L~ are~
the pH, the solid~ content (%) and the minimum fil~
forming temperature (MFFT in C), that is to say the lowest temperature at which a film is obtained. A wet abrasion resistance (WAR) test is performed on the `~
20 paints P2, P3 and P~, which i~ performed with the aid o~ ;
a C-- abrasiometer according to DIN Standard 53778. ~he WAR is evaluated as the number of cycles at the end of which the paint i8 eroded.
The results obtained are collated in Table 1 below insofar as the media are concerned and in Table 2 below in~ofar a~ the paints are concerned.
'' ', :' ' ''`""
`' ,`'`'',''`.",`'~``'`
`;~
, ' ' '~
` 2 1 3 5 ~ ~ o TABLE 1 .
- ., .;,..........
~-di~= ~ pH SC ~ (=P- ~) 5 Z8 d/ MFFT
._ ,',, ` ',- ~.'`~
L? 7.7 47.9 2080 0.75 0 ; ` ~
.~ ,, _ _ - ___ -', ,. . ' ` ,' -.-.'-.
L3 8 47.8 1200 0.65 0 , . .__ Ls 7.8 48.0 600 1.05 0 , ....... . ,__ ' `,~
,__ "'~
Paint Medi~ V S 28 d/ WAR (~o.
.___. employed (mPa 8)55C of cyrle~) Pl L2 4080 1 3910 ._ p3 L3 4440 1.15 1370 .
_ .~
P~ L~ 4120 1.1 3400 , __ _ ,,_, ,~,__ ~ .. ,.. ,,.,,,,", Po LA 3560 1.05 2550 Paint Po i8 a control paint prepared only with the medium LA.
From Tables 1 and 2 above it appears that paints which have satis$actory viscosities and which remain perfectly stable at the end of the 28 days at 55C are obtained. ~:
It is noted, furthermore, that the addition of binder B with Tg = 0C greatly improves the WAR.
~ ' : ~! . , . ~ .!
Claims (3)
1. Medium for a coating composition based on film-forming latices prepared from unsaturated ethylenic monomers, characterized in that the said medium comprises, per 100 parts by weight of latex A (calculated on the basis of the solids content) which has a particle size of between 100 and 500 nm, from 0.1 to 100 parts by weight of latex B (calculated on the basis of the solids content) which has a particle size of between 5 and 40 nm.
2. Medium according to claim 1, characterized in that, per 100 parts of latex A which has a particle size of between 120 and 300 nm, the said medium comprises 0.5 to 20 parts, preferably from 1 to 10 parts of latex B which has a particle size of between 10 and 30 nm.
3. Medium for a coating composition according to claim 1 or 2, characterized in that it is employed in compositions for paper coating, for paint, for varnish, for textile finishing, for wood coating, in adhesive compositions, in pressure-sensitive adhesive compositions and in coating compositions for cement mortar.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9313416 | 1993-11-10 | ||
FR9313416A FR2712296B1 (en) | 1993-11-10 | 1993-11-10 | Latex binder for coating composition. |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2135450A1 true CA2135450A1 (en) | 1995-05-11 |
Family
ID=9452725
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2135450 Abandoned CA2135450A1 (en) | 1993-11-10 | 1994-11-09 | Latex medium for a coating composition |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0652269A1 (en) |
CA (1) | CA2135450A1 (en) |
FI (1) | FI945278A (en) |
FR (1) | FR2712296B1 (en) |
NO (1) | NO944282L (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2289991A1 (en) * | 2009-08-26 | 2011-03-02 | University Of Waterloo | Nano-sized diene-based polymer latex particles |
US9598616B2 (en) | 2013-04-25 | 2017-03-21 | Toyo Ink Sc Holdings Co., Ltd. | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using same |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE9419333U1 (en) * | 1994-12-02 | 1995-01-26 | Lefatex Chemie GmbH, 41379 Brüggen | Coating agents for paper surfaces |
AUPO216396A0 (en) * | 1996-09-06 | 1996-10-03 | Ici Australia Operations Proprietary Limited | Stain resistant water-borne paint |
GB9823499D0 (en) * | 1998-10-27 | 1998-12-23 | Proman Chem Ltd | Barrier coatings |
ATE424438T1 (en) * | 2001-01-17 | 2009-03-15 | Dow Global Technologies Inc | AQUEOUS BIMODAL PLASTIC DISPERSIONS |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3017543A1 (en) * | 1980-05-08 | 1981-11-26 | Bayer Ag, 5090 Leverkusen | AQUEOUS DISPERSIONS BASED ON (METH) ACRYLIC ACID ALKYLESTER POLYMERISATES WITH TWO EXCELLENT, PRACTICALLY NOT OVERLAPPING MAXIMAS IN PARTICLE SIZE DISTRIBUTION WITHIN SPECIFIC PARTICLE LARGE RANGE |
JPS5849823A (en) * | 1981-09-18 | 1983-03-24 | Matsushita Electric Ind Co Ltd | Hot water feeder |
-
1993
- 1993-11-10 FR FR9313416A patent/FR2712296B1/en not_active Expired - Fee Related
-
1994
- 1994-10-21 EP EP94402370A patent/EP0652269A1/en not_active Withdrawn
- 1994-11-09 FI FI945278A patent/FI945278A/en not_active Application Discontinuation
- 1994-11-09 CA CA 2135450 patent/CA2135450A1/en not_active Abandoned
- 1994-11-10 NO NO944282A patent/NO944282L/en unknown
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2289991A1 (en) * | 2009-08-26 | 2011-03-02 | University Of Waterloo | Nano-sized diene-based polymer latex particles |
EP2470577A1 (en) * | 2009-08-26 | 2012-07-04 | University Of Waterloo | Nano-sized diene-based polymer latex particles |
EP2470577A4 (en) * | 2009-08-26 | 2013-04-17 | Univ Waterloo | Nano-sized diene-based polymer latex particles |
US9598616B2 (en) | 2013-04-25 | 2017-03-21 | Toyo Ink Sc Holdings Co., Ltd. | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using same |
Also Published As
Publication number | Publication date |
---|---|
NO944282L (en) | 1995-05-11 |
NO944282D0 (en) | 1994-11-10 |
FI945278A (en) | 1995-05-11 |
EP0652269A1 (en) | 1995-05-10 |
FI945278A0 (en) | 1994-11-09 |
FR2712296A1 (en) | 1995-05-19 |
FR2712296B1 (en) | 1996-01-12 |
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