CN115427518A - 水性分散体遮光颜料颗粒 - Google Patents
水性分散体遮光颜料颗粒 Download PDFInfo
- Publication number
- CN115427518A CN115427518A CN202180027863.6A CN202180027863A CN115427518A CN 115427518 A CN115427518 A CN 115427518A CN 202180027863 A CN202180027863 A CN 202180027863A CN 115427518 A CN115427518 A CN 115427518A
- Authority
- CN
- China
- Prior art keywords
- range
- weight
- multistage
- structural units
- polymeric particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 109
- 239000006185 dispersion Substances 0.000 title claims abstract description 22
- 239000000049 pigment Substances 0.000 title description 10
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000004606 Fillers/Extenders Substances 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 6
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- -1 defoamers Substances 0.000 claims description 4
- 239000006254 rheological additive Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 239000001023 inorganic pigment Substances 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 238000009472 formulation Methods 0.000 abstract description 19
- 239000003973 paint Substances 0.000 abstract description 18
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229920005787 opaque polymer Polymers 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000009991 scouring Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920005789 ACRONAL® acrylic binder Polymers 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- 229920005788 AQACell® HIDE 6299 na Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001093575 Alma Species 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 239000004318 erythorbic acid Substances 0.000 description 1
- TVFJAZCVMOXQRK-UHFFFAOYSA-N ethenyl 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC(=O)OC=C TVFJAZCVMOXQRK-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/022—Emulsions, e.g. oil in water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/45—Anti-settling agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Paints Or Removers (AREA)
Abstract
本发明涉及包含第一多级聚合物颗粒和第二多级聚合物颗粒的水性分散体的水性组合物，其中该第一聚合物颗粒和该第二聚合物颗粒各自包含水吸留芯和高Tg聚合物外壳，其中该第二多级聚合物颗粒还包含叠加在该外壳上的聚合物粘结剂层。本发明的组合物可用于降低油漆配方中TiO2的载量，同时产生具有优异遮盖力和耐擦洗性的涂层。
Description
背景技术
本发明涉及遮光颜料颗粒的水性分散体。本发明的组合物可用于降低无机颜料诸如二氧化钛在油漆配方中的载量，同时保持或改善遮盖性。
二氧化钛(TiO2)由于其非常高的折射率而成为油漆工业中最常用的遮光颜料。然而，TiO2是油漆中最昂贵的组分；此外，其制造需要高能耗，并带来潜在的环境危害风险。由于世界各地的监管机构正在推动旨在为包含TiO2的产品贴上警告标签的立法，因此大幅降低消费产品诸如建筑油漆中TiO2的浓度变得更加紧迫。
在不存在TiO2的情况下，可以通过用大量增量剂代替TiO2来获得高于临界颜料体积浓度的配方，从而在油漆中实现可接受的遮光性能(遮盖力)。然而，由于可接受的不透明度是通过产生气隙来实现的，而气隙是由不足以形成有效膜的粘结剂产生，因此所得涂层的耐擦洗性差。
尽管遮光性能也可以通过添加不透明聚合物颗粒来增强，但是这些有机遮光剂提高不透明度的能力受到它们固有的较低折射率以及在高浓度下伴随的较差涂层特性的限制。因此，不透明聚合物颗粒不是TiO2的替代品；它们的使用仅限于辅助作用，以降低实现可接受的遮盖力和保持建筑涂料性能所需的TiO2载量。
因此，发现具有可接受的遮盖力和耐擦洗性能的基本上不含TiO2的着色涂料组合物将是本领域的进步。
发明内容
本发明通过提供包含第一多级聚合物颗粒和第二多级聚合物颗粒的水性分散体的水性组合物来解决本领域的需要，其中第一聚合物颗粒和第二聚合物颗粒各自包含：
a)水吸留芯，该水吸留芯包含20重量％至60重量％的羧酸单体的盐的结构单元和40重量％至80重量％的非离子单烯属不饱和单体的结构单元；以及
b)聚合物外壳，该聚合物外壳具有在60℃至120℃的范围内的Tg；
其中第二多级聚合物颗粒还包含：
c)叠加在外壳上的聚合物粘结剂层，该聚合物粘结剂层具有不大于35℃的Tg并且包含至少一种单烯属不饱和单体的结构单元；
其中第一多级聚合物颗粒和第二多级聚合物颗粒中水吸留芯与外壳中的单体结构单元的重量-重量比在1:10至1:20的范围内；
第二多级聚合物颗粒中聚合物粘结剂与外壳和芯中单体结构单元之和的重量-重量比在1:1至3.5:1的范围内；
第一多级聚合物颗粒与第二多级聚合物颗粒的重量-重量比在0.15:1至1.0:1的范围内；
第一聚合物颗粒的z-平均粒度在200nm至2000nm的范围内；并且
第二聚合物颗粒的z-平均粒度在300nm至750nm的范围内。
本发明通过提供一种组合物解决了本领域的需要，该组合物基本上减少，并且在一些情况下，消除了在油漆配方中作为遮光颜料的TiO2的需要。
具体实施方式
本发明是包含第一第二多级聚合物颗粒的水性分散体的水性组合物，其中第一聚合物颗粒和第二聚合物颗粒各自包含：
a)水吸留芯，该水吸留芯包含20重量％至60重量％的羧酸单体的盐的结构单元和40重量％至80重量％的非离子单烯属不饱和单体的结构单元；以及
b)聚合物外壳，该聚合物外壳具有在60℃至120℃的范围内的Tg；
其中第二多级聚合物颗粒还包含：
c)叠加在外壳上的聚合物粘结剂层，该聚合物粘结剂层具有不大于35℃的Tg并且包含至少一种单烯属不饱和单体的结构单元；
其中第一多级聚合物颗粒和第二多级聚合物颗粒中水吸留芯与外壳中的单体结构单元的重量-重量比在1:10至1:20的范围内；
第二多级聚合物颗粒中聚合物粘结剂与外壳和芯中单体结构单元之和的重量-重量比在1:1至3.5:1的范围内；
第一多级聚合物颗粒与第二多级聚合物颗粒的重量-重量比在0.15:1至1.0:1的范围内；
第一聚合物颗粒的z-平均粒度在200nm至2000nm的范围内；并且
第二聚合物颗粒的z-平均粒度在300nm至750nm的范围内。
基于芯中单体的结构单元的重量，水吸留芯包含从20重量％，优选地从25重量％，更优选地从30重量％，并且最优选地从32重量％至60重量％，优选地至50重量％，更优选地至40重量％，并且最优选地至36重量％的羧酸单体的盐的结构单元。
如本文所用，术语“结构单元”是指所述单体在聚合后的残余物。例如，甲基丙烯酸盐的结构单元，其中M+是抗衡离子，优选锂、钠或钾抗衡离子，如所示：
合适的羧酸单体的示例包括丙烯酸、甲基丙烯酸、衣康酸和马来酸。
基于芯中单体的结构单元的重量，水吸留芯还包含从40重量％，优选地从50重量％，更优选地从55重量％，更优选地从60重量％，并且最优选地从64重量％至80重量％，优选地至75重量％，更优选地至70重量％，并且最优选地至68重量％的非离子单烯属不饱和单体的结构单元。非离子单烯属不饱和单体的示例包括一种或多种丙烯酸酯和/或甲基丙烯酸酯，诸如丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸异丁酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯和甲基丙烯酸环己酯；以及一种或多种单烯属不饱和芳族化合物，诸如苯乙烯、α-甲基苯乙烯和4-叔丁基苯乙烯。优选的非离子单烯属不饱和单体是甲基丙烯酸甲酯。
第一聚合物颗粒和第二聚合物颗粒的聚合物外壳优选地具有不小于80℃，更优选地不小于90℃，最优选地不小于95℃，优选地不大于115℃，最优选地不大于110℃的Tg。如本文所用，Tg是指通过Fox方程计算的玻璃化转变温度。
优选地，第一聚合物颗粒和第二聚合物颗粒的外壳包含甲基丙烯酸甲酯、苯乙烯、α-甲基苯乙烯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯或甲基丙烯酸环己酯的结构单元。在一个实施方案中，外壳包含至少80重量％，更优选地至少90重量％，最优选地至少95重量％的苯乙烯结构单元。在另一个实施方案中，外壳包含89重量％至93重量％的苯乙烯结构单元和7重量％至11重量％的甲基丙烯酸甲酯(4重量％至5重量％)、甲基丙烯酸环己酯(0.9重量％至2重量％)、甲基丙烯酸(2重量％至3重量％)和多烯键属不饱和单体甲基丙烯酸烯丙酯(ALMA，0.1重量％至0.5重量％)中任一种或全部的结构单元。
第一聚合物颗粒和第二聚合物颗粒的聚合物外壳还可以进一步包含其他多烯键属不饱和单体，诸如二乙烯基苯(DVB)、三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)或三羟甲基丙烷三丙烯酸酯(TMPTA)的结构单元。
如本文所用，“聚合物粘结剂”是指在有或没有聚结剂的情况下在所需基底上成膜的聚合物材料。在一个方面，通过Fox方程计算的聚合物粘结剂的Tg不大于25℃；在另一方面，不大于15℃，在另一方面，不大于10℃，在另一方面，不小于-20℃，在另一方面，不小于-10℃。
合适的聚合物粘结剂材料的示例包括丙烯酸类、苯乙烯-丙烯酸类、乙烯基酯诸如乙酸乙烯酯和新癸酸乙烯酯，以及乙烯基酯-乙烯聚合物粘结剂。包含甲基丙烯酸甲酯的结构单元和一种或多种丙烯酸酯诸如丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯或丙烯酸2-乙基己酯的结构单元的丙烯酸类粘结剂是特别优选的，苯乙烯-丙烯酸类粘结剂也是如此。
优选地，第一多级聚合物颗粒和第二多级聚合物颗粒中的芯与外壳的单体结构单元的重量-重量比在1:12至1:16的范围内。优选地，第二多级聚合物颗粒中聚合物粘结剂与芯和外壳的单体结构单元之和的重量-重量比在从1.2:1，更优选地从1.5:1，并且最优选地从1.8:1至优选地3.0:1，更优选地至2.5:1，并且最优选地至2.2:1的范围内。
优选地，第一多级聚合物颗粒与第二多级聚合物颗粒的重量-重量比在从0.30:1，更优选地从0.40:1，更优选地从0.50:1，最优选地从0.55:1至优选地0.9:1，更优选地至0.80:1，更优选地至0.70:1，最优选地至0.65:1的范围内。
在一个方面，第一聚合物颗粒的z-平均粒度优选地在950nm至2000nm的范围内；在另一方面，第一聚合物颗粒的z-平均粒度优选地在从300nm，更优选地从350nm，最优选地从375nm至优选地600nm，更优选地至500nm，最优选地至425nm的范围内。如本文所用，z平均粒度是指通过动态光散射，例如通过BI-90Plus粒度分析仪(Brookhaven)测定的粒度。
第二聚合物颗粒的z-平均粒度在从400nm，更优选地从450nm，最优选地从475nm至优选地700nm，更优选地至600nm，并且最优选地至550nm的范围内。
本发明的组合物可以通过将第一多级聚合物颗粒的水性分散体与第二多级聚合物颗粒的水性分散体混合来方便地制备。第一多级聚合物颗粒的水性分散体可以通过本领域已知的方法制备，例如，如US 6,020,435和US2020/0071439A1中所公开。可商购获得的第一多级聚合物颗粒的分散体的示例包括ROPAQUETM超不透明聚合物、AQACell HIDE 6299不透明聚合物和ROPAQUETMTH-2000中空球颜料。(ROPAQUE是The Dow Chemical Company或其附属公司的商标)。第二多级聚合物颗粒的水性分散体可如US 7,691,942 B2中所述制备。制备第二多级聚合物颗粒的分散体的优选方法的示例示于实施例部分的中间体实施例中。
本发明的第一多级聚合物颗粒和第二多级聚合物颗粒的水性分散体在将分散体施加到基底上随后蒸发吸留在芯中的水时形成不透明的聚合物颗粒或中空球聚合物颗粒(也称为OP或HSP)。因此，本发明的组合物可用作油漆配方中的遮光剂和粘结剂，特别是需要减少，甚至消除TiO2载量的油漆配方。令人惊奇地发现，与包含不透明聚合物颗粒和未叠加在不透明聚合物上的不同粘结剂颗粒的分散体相比，涂覆粘结剂的不透明聚合物颗粒和未涂覆粘结剂的不透明聚合物颗粒的组合提供了优异的遮盖力和耐擦洗性。
组合物可以包括其他材料，诸如流变改性剂、分散剂、消泡剂、表面活性剂、聚结剂、增量剂和无机颜料。ZnO2是特别有用的颜料，其可以在本发明的组合物中用作TiO2的替代物以及第一多级聚合物颗粒和第二多级聚合物颗粒的补充或部分替代物。优选地，本发明的组合物包含小于1重量％的TiO2。在另一方面，组合物包含0重量％的TiO2。
Kubelka-Munk散射系数(S/mil)计算
遮盖性能通过S/mil表征如下。对于黑色释放图表上的每种油漆，使用1.5密耳Bird刮涂棒制备三个刮涂物，使用25密耳Bird刮涂棒制备一个刮涂物。使刮涂物干燥过夜。使用模板，在每个图表上用X-ACTO刀具切出3.25”x4”的矩形。使用XRite反射计在每个划线区域中收集五个重复反射率测量值。在刮涂物的五个不同区域中测量y-反射率，并记录平均y-反射率。Kubelka-Munk遮盖力值S由以下等式给出
其中X是薄膜的平均膜厚度，R是厚膜(25密耳)的平均反射率，RB是薄膜(1.5密耳)在黑色上的平均反射率。X可由膜的重量(Wpf)、干膜的密度(D)和膜面积(A)计算。3.25″X4″模板的膜面积为13in2。
耐擦洗性测量
耐擦洗性测试基于ISO 11998。在温度和湿度受控的房间中，用20密耳Dow涂覆器在黑色乙烯基擦洗图表上进行刮涂，然后干燥7天。在擦洗测试之前和之后(并且干燥过夜)对刮涂图表进行称重，以确定在进行擦洗测试之前在分析天平上的重量损失。在PacificScientific磨耗试验机上进行擦洗测试，使用0.25％DS-4作为擦洗介质，Scotch Brite7448+超细手工研磨垫作为擦洗垫。在测试之前，用软刷将擦洗介质涂抹在涂层表面上，并用擦洗介质将擦洗垫饱和至最终总质量为4g。擦洗测试进行200个循环，然后立即用水冲洗擦洗过的面板。使面板干燥过夜并将图表重新称重。然后使用重量损失计算膜厚度损失。
PVC计算
颜料体积浓度通过以下公式计算：
其中粘结剂固体是指来自中间体实施例的苯乙烯-丙烯酸类粘结剂层的聚合物的贡献，或指来自Acronal S 559苯乙烯丙烯酸类粘结剂的粘结剂，或两者。OP是指第一多级聚合物颗粒和第二多级聚合物颗粒的芯：外壳部分的体积的贡献。
实施例
中间体实施例-涂覆粘结剂的多级聚合物颗粒的水性分散体的制备
在以下实施例中，芯#1是指基本上如US 6,020,435中所述制备的聚合物颗粒(66MMA/34MAA，固体31.9％，135nm的z-平均粒度)的水性分散体。
5升四颈圆底烧瓶装配备有桨式搅拌器、温度计、N2入口和回流冷凝器。将DI水(475g)添加到釜中并在N2下加热至89℃。立即将过硫酸钠(NaPS，3g于25g水中)添加到容器中，随后添加芯#1(125g)。然后将通过混合DI水(125.0g)、Disponil FES-32乳化剂(10.0g)、苯乙烯(424.2g)、甲基丙烯酸(7.0g)、亚麻籽油脂肪酸(2.8g)、丙烯腈(112.0g)和二乙烯基苯(14.0g)制备的单体乳液1(ME1)在60分钟内添加到釜中。使反应混合物的温度在15分钟后升至84℃，并在25分钟后升至92℃。在ME1进料完成后，将反应冷却至60℃。
当釜温度达到80℃时，将硫酸亚铁和EDTA的水性混合物(20g，0.1重量％的FeSO4，1重量％的EDTA)添加到釜中。当釜温度达到60℃时，将包括叔丁基过氧化氢(t-BHP 1.9g)和与DI水(100g)混合的NaPS(5.0g)的溶液的共进料，连同异抗坏血酸(IAA，2.6g于100g水中)的单独溶液以1.20g/min的速率同时添加到釜中。在装入共进料溶液两分钟后，将通过混合DI水(240g)、Disponil FES-32乳化剂(17.0g)、丙烯酸丁酯(431.46g)、甲基丙烯酸甲酯(430.54g)、丙烯酸2-乙基己酯(124.44g)、甲基丙烯酸乙酰乙酰氧基乙酯(25.5g)和甲基丙烯酸(7.96g)制备的ME2在60分钟内添加到釜中，同时在不提供任何外部热量的情况下使温度升至86℃。在ME2添加完成后，停止添加共进料溶液并将批料保持在80℃至86℃下5分钟。然后将与DI水(5.0g)混合的NH4OH溶液(5g，28重量％水溶液)连同热(90℃)DI水(175g)添加到釜中。
将通过混合DI水(54.0g)、Disponil FES-32乳化剂(3.0g)、丙烯酸丁酯(104.4g)、甲基丙烯酸甲酯(75.6g)和4-羟基TEMPO(3.0g)制备的ME3在5分钟内添加到釜中。在ME3进料添加完成之后，立即将与DI水(35g)混合的NH4OH(35.0g，28重量％水溶液)在2分钟内添加到釜中。当NH4OH添加完成时，将批料保持5分钟。以1.2g/min重新开始添加共进料溶液直至完成，随后将分散体冷却至25℃。在冷却时，将包括t-BHP(1.5g)于DI水(25g)中的溶液以及IAA(0.7g)于水(25g)中的单独溶液的附加共进料以1.30g/min的速率同时添加到釜中。在第二共进料的添加完成之后，将分散体过滤以除去任何凝结物。过滤的分散体具有48.7％的固体含量。测量的S/Mil为1.03，塌缩率为0.0％。
表1示出了具有第一多级聚合物颗粒和第二多级聚合物颗粒的油漆配方。在下表中，不透明聚合物是指ROPAQUETMUltra EF不透明聚合物(30重量％固体)，消泡剂是指Foamstar A34消泡剂，聚结剂是指Texanol聚结剂，增稠剂是指Natrosol 250 MHR增稠剂，ZnO2是指ZOCO 101 ZnO2，增量剂是指并且分散剂是指TAMOLTM851分散剂。(TAMOL是The DowChemical Company或其附属公司的商标)。在每个配方中，固体体积为31.8％。
表1-实施例油漆配方1至3
表2A和表2B示出了比较例油漆配方。粘结剂是指Acronal S 559苯乙烯丙烯酸粘结剂(50重量％固体)，TiO2是指Kronos 4311 TiO2浆液(76.5重量％)，增量剂是指OmyacarbUF CaCO3增量剂。
表2A-比较例油漆配方1至3的油漆配方。
| 成分(g) | 比较例1 | 比较例2 | 比较例3 |
| 粘结剂 | 282.76 | 282.91 | 282.56 |
| 不透明聚合物 | 267.65 | 241.19 | 214.06 |
| 水 | 178.50 | 139.07 | 101.20 |
| 消泡剂 | 0.60 | 0.60 | 0.60 |
| 增稠剂 | 121.06 | 121.17 | 121.02 |
| 水 | - | 49.66 | 99.20 |
| ZnO<sub>2</sub> | - | 73.50 | 146.81 |
| 分散剂 | - | 2.45 | 4.89 |
| 特性 | |||
| 总体积(mL) | 1000.00 | 1000.00 | 1000.00 |
| 总重量(g) | 850.57 | 910.55 | 970.34 |
| 总PVC | 50.00 | 50.00 | 50.00 |
| ZnO<sub>2</sub> PVC | 0.00 | 5.00 | 10.00 |
| OP PVC | 50.00 | 45.0 | 40.00 |
表2B-比较例油漆配方4至7的配方
表3示出了实施例和比较例油漆配方的S/mil和耐擦洗性数据。
| 实施例编号 | S/mil | 膜损失(μm) |
| 实施例1 | 4.87 | 3.5 |
| 实施例2 | 6.12 | 4.4 |
| 实施例3 | 7.43 | 6.9 |
| 比较例1 | 2.42 | 3.5 |
| 比较例2 | 2.61 | 8.7 |
| 比较例3 | 2.71 | 10.7 |
| 比较例4 | 2.3 | 42.2 |
| 比较例5 | 5.19 | 43.9 |
| 比较例6 | 7.02 | 35.8 |
| 比较例7 | 3.19 | 22.3 |
数据显示，与缺少一种或两种类型的遮光颜料的比较例配方相比，包含第一多级聚合物颗粒和第二多级聚合物颗粒(不透明聚合物和中间体1)的分散体的油漆配方具有优异的遮盖力和耐擦洗性。数据还表明，与包含TiO2和未叠加在不透明聚合物颗粒上的粘结剂的配方相比，包含ZnO2与不透明聚合物和中间体1(实施例2和实施例3)组合的配方显示出优异的遮盖力和耐擦洗性。
Claims (11)
1.一种水性组合物，所述水性组合物包含第一多级聚合物颗粒和第二多级聚合物颗粒的水性分散体，其中所述第一聚合物颗粒和所述第二聚合物颗粒各自包含：
a)水吸留芯，所述水吸留芯包含20重量％至60重量％的羧酸单体的盐的结构单元和40重量％至80重量％的非离子单烯属不饱和单体的结构单元；以及
b)聚合物外壳，所述聚合物外壳具有在60℃至120℃的范围内的Tg；
其中所述第二多级聚合物颗粒还包含：
c)叠加在所述外壳上的聚合物粘结剂层，所述聚合物粘结剂层具有不大于35℃的Tg并且包含至少一种单烯属不饱和单体的结构单元；
其中所述第一多级聚合物颗粒和所述第二多级聚合物颗粒中所述水吸留芯与所述外壳中的单体结构单元的重量-重量比在1:10至1:20的范围内；
所述第二多级聚合物颗粒中所述聚合物粘结剂与所述外壳和所述芯中单体结构单元之和的重量-重量比在1:1至3.5:1的范围内；
所述第一多级聚合物颗粒与所述第二多级聚合物颗粒的重量-重量比在0.15:1至1.0:1的范围内；
所述第一聚合物颗粒的z-平均粒度在200nm至2000nm的范围内；并且
所述第二聚合物颗粒的z-平均粒度在300nm至750nm的范围内。
2.根据权利要求1所述的组合物，其中所述多级聚合物颗粒外壳包含至少80重量％的苯乙烯结构单元并且具有在90℃至115℃范围内的Tg；其中基于所述多级聚合物颗粒水吸留芯中单体结构单元的重量，所述芯包含30重量％至50重量％的羧酸单体的盐的结构单元和50重量％至70重量％的所述非离子单烯属不饱和单体的结构单元。
3.根据权利要求2所述的组合物，其中所述非离子单烯属不饱和单体是选自由以下组成的组的一种或多种丙烯酸酯或甲基丙烯酸酯：丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、丙烯酸叔丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸异丁酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯和甲基丙烯酸环己酯；以及选自由苯乙烯、α-甲基苯乙烯和4-叔丁基苯乙烯组成的组的单烯属不饱和芳族化合物。
4.根据权利要求3所述的组合物，其中所述外壳包含89重量％至93重量％的苯乙烯结构单元和7重量％至11重量％的选自由甲基丙烯酸甲酯、甲基丙烯酸环己酯、甲基丙烯酸和甲基丙烯酸烯丙酯组成的组的一种或多种附加单体结构单元。
5.根据权利要求3所述的组合物，其中所述外壳包含89重量％至93重量％的苯乙烯结构单元，以及4重量％至5重量％的甲基丙烯酸甲酯结构单元、0.9重量％至2重量％的甲基丙烯酸环己酯结构单元、2重量％至3重量％的甲基丙烯酸结构单元和0.1重量％至0.5重量％的甲基丙烯酸烯丙酯结构单元；其中所述羧酸单体的盐是甲基丙烯酸的盐；其中所述粘结剂是Tg在-20℃至15℃范围内的丙烯酸类或苯乙烯丙烯酸类粘结剂。
6.根据权利要求5所述的组合物，其中所述第二多级聚合物颗粒中所述聚合物粘结剂与所述芯和所述外壳的单体结构单元之和的重量-重量比在1.5:1至2.5:1的范围内；并且所述第一多级聚合物颗粒和所述第二多级聚合物颗粒中的所述芯与所述外壳的单体结构单元的重量-重量比在1:12至1:16的范围内；其中所述第一多级聚合物颗粒的z-平均粒度在350nm至500nm的范围内或在950nm至2000nm的范围内；所述第二多级聚合物颗粒的z-平均粒度在450nm至600nm的范围内；并且所述第一多级聚合物颗粒与所述第二多级聚合物颗粒的重量-重量比在0.30:1至0.7:1的范围内。
7.根据权利要求6所述的组合物，其中所述第一多级聚合物颗粒的z-平均粒度在375nm至425nm的范围内；所述第二多级聚合物颗粒的z-平均粒度在475nm至550nm的范围内；并且所述第一多级聚合物颗粒与所述第二多级聚合物颗粒的重量-重量比在0.50:1至0.65:1的范围内。
8.根据权利要求1所述的组合物，所述组合物还包含流变改性剂和一种或多种选自由分散剂、消泡剂、表面活性剂、聚结剂、增量剂和无机颜料组成的组的组分。
9.根据权利要求7所述的组合物，所述组合物包含流变改性剂、分散剂、消泡剂、表面活性剂、为ZnO2的无机颜料和基于所述组合物的重量小于1重量％的TiO2。
10.根据权利要求7所述的组合物，所述组合物包含流变改性剂、分散剂、消泡剂、表面活性剂、为ZnO2的无机颜料和0重量％的TiO2。
11.根据权利要求3所述的组合物，其中所述第二多级聚合物颗粒中所述聚合物粘结剂与所述芯和所述外壳的单体结构单元之和的重量-重量比在1.5:1至2.5:1的范围内；并且所述第一多级聚合物颗粒和所述第二多级聚合物颗粒中的所述芯与所述外壳的单体结构单元的重量-重量比在1:12至1:16的范围内；其中所述第一多级聚合物颗粒的z-平均粒度在350nm至500nm的范围内或在950nm至2000nm的范围内；所述第二多级聚合物颗粒的z-平均粒度在450nm至600nm的范围内；并且所述第一多级聚合物颗粒与所述第二多级聚合物颗粒的重量-重量比在0.30:1至0.7:1的范围内。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202063021919P | 2020-05-08 | 2020-05-08 | |
| US63/021919 | 2020-05-08 | ||
| PCT/US2021/027659 WO2021225769A1 (en) | 2020-05-08 | 2021-04-16 | Aqueous dispersion opacifying pigment particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115427518A true CN115427518A (zh) | 2022-12-02 |
| CN115427518B CN115427518B (zh) | 2024-05-28 |
Family
ID=76250415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180027863.6A Active CN115427518B (zh) | 2020-05-08 | 2021-04-16 | 水性分散体遮光颜料颗粒 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20230167309A1 (zh) |
| EP (1) | EP4146745A1 (zh) |
| KR (1) | KR20230008771A (zh) |
| CN (1) | CN115427518B (zh) |
| AU (1) | AU2021266657A1 (zh) |
| BR (1) | BR112022020778A2 (zh) |
| CA (1) | CA3174250A1 (zh) |
| WO (1) | WO2021225769A1 (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA3238443A1 (en) | 2021-11-22 | 2023-05-25 | Michael W. Leonard | Aqueous dispersion of opacifying pigment-binder hybrid polymer particles |
| AU2022394524A1 (en) * | 2021-11-22 | 2024-06-20 | Rohm And Haas Company | Method for preparing opacifying pigment-binder hybrid polymer particles |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885320A (en) * | 1987-11-05 | 1989-12-05 | Union Oil Company Of California | Polymeric opaque particles and process for making same |
| CA2253073A1 (en) * | 1997-11-05 | 1999-05-05 | Rohm And Haas Company | Process for preparing polymer emulsions and polymers formed therefrom |
| EP1754729A1 (en) * | 2005-08-19 | 2007-02-21 | Rohm and Haas Company | Aqueous dispersion of polymeric particles |
| CN106543848A (zh) * | 2015-09-17 | 2017-03-29 | 罗门哈斯公司 | 具有磷酸官能化胶乳粘合剂和缔合型增稠剂的色漆配制品 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0721548A2 (pt) * | 2006-11-17 | 2014-02-18 | Basf Se | Formulação aquosa, uso de pelo menos uma formulação, processo para revestir uma superfície, superfície revestida, e, processo para preparar uma formulação aquosa. |
| EP2161304B1 (en) * | 2008-09-04 | 2014-04-23 | Rohm and Haas Company | Opacifying pigment particle |
| CA2912294C (en) * | 2014-12-01 | 2023-01-03 | Dow Global Technologies Llc | Phosphorus acid functionalized opaque polymer |
| CN110872366B (zh) | 2018-09-04 | 2023-10-20 | 罗门哈斯公司 | 用于制备多级聚合物颗粒的水分散体的方法 |
-
2021
- 2021-04-16 AU AU2021266657A patent/AU2021266657A1/en active Pending
- 2021-04-16 WO PCT/US2021/027659 patent/WO2021225769A1/en unknown
- 2021-04-16 US US17/921,182 patent/US20230167309A1/en active Pending
- 2021-04-16 CA CA3174250A patent/CA3174250A1/en active Pending
- 2021-04-16 BR BR112022020778A patent/BR112022020778A2/pt not_active Application Discontinuation
- 2021-04-16 KR KR1020227042278A patent/KR20230008771A/ko active Search and Examination
- 2021-04-16 CN CN202180027863.6A patent/CN115427518B/zh active Active
- 2021-04-16 EP EP21729673.0A patent/EP4146745A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4885320A (en) * | 1987-11-05 | 1989-12-05 | Union Oil Company Of California | Polymeric opaque particles and process for making same |
| CA2253073A1 (en) * | 1997-11-05 | 1999-05-05 | Rohm And Haas Company | Process for preparing polymer emulsions and polymers formed therefrom |
| EP1754729A1 (en) * | 2005-08-19 | 2007-02-21 | Rohm and Haas Company | Aqueous dispersion of polymeric particles |
| CN106543848A (zh) * | 2015-09-17 | 2017-03-29 | 罗门哈斯公司 | 具有磷酸官能化胶乳粘合剂和缔合型增稠剂的色漆配制品 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP4146745A1 (en) | 2023-03-15 |
| AU2021266657A1 (en) | 2022-12-08 |
| WO2021225769A1 (en) | 2021-11-11 |
| US20230167309A1 (en) | 2023-06-01 |
| BR112022020778A2 (pt) | 2022-11-29 |
| CA3174250A1 (en) | 2021-11-11 |
| KR20230008771A (ko) | 2023-01-16 |
| CN115427518B (zh) | 2024-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102128766B1 (ko) | 이모드성 흡착 라텍스 | |
| EP2009072B1 (en) | Aqueous polymeric composition | |
| EP3299400B1 (en) | Latex functionalized with structural units of an amino acid | |
| CN115427518B (zh) | 水性分散体遮光颜料颗粒 | |
| CA2120723A1 (en) | Water-dilutable emulsion polymerisate, process for producing it, aqueous coating composition based on the emulsion polymer and its use as a grinding and dispersing resin and as a binder for physically-drying paints | |
| US20120214928A1 (en) | Waterborne compositions and their use as paints and stains | |
| AU2017265159B2 (en) | Aqueous dispersion of fluoralkylated polymer particles with acorn morphology | |
| EP3339339B1 (en) | Latex functionalized with structural units of an arginine functionalized monomer | |
| EP3289030B1 (en) | Low sheen paint composition with effective opacity | |
| AU2021357551A1 (en) | Aqueous dispersion of opacifying pigment particles and colorant | |
| AU2021340549A1 (en) | Aqueous dispersion opacifying pigment-binder hybrid polymer particles | |
| AU2020461035A1 (en) | Aqueous dispersion of polymer particles, microspheres, and colloidal silica particles | |
| CA3185914A1 (en) | Aqueous dispersion of polymer particles and microspheres | |
| CN116323832A (zh) | 乳液聚合物及其制备方法 | |
| CN113811551A (zh) | 包括多级聚合物的水性分散体以及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |