CN1989162B - Polymeric particles - Google Patents
Polymeric particles Download PDFInfo
- Publication number
- CN1989162B CN1989162B CN200580024497XA CN200580024497A CN1989162B CN 1989162 B CN1989162 B CN 1989162B CN 200580024497X A CN200580024497X A CN 200580024497XA CN 200580024497 A CN200580024497 A CN 200580024497A CN 1989162 B CN1989162 B CN 1989162B
- Authority
- CN
- China
- Prior art keywords
- monomer
- polymer
- polymer beads
- secondary particle
- ethylenic
- 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.)
- Expired - Fee Related
Links
- 239000002245 particle Substances 0.000 title claims abstract description 55
- 239000000178 monomer Substances 0.000 claims abstract description 138
- 239000011159 matrix material Substances 0.000 claims abstract description 74
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 51
- 239000011163 secondary particle Substances 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 21
- 229920001519 homopolymer Polymers 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 56
- 239000000463 material Substances 0.000 claims description 55
- 239000011324 bead Substances 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 35
- 150000002500 ions Chemical class 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 22
- 239000000975 dye Substances 0.000 claims description 22
- -1 stearyl acrylate ester Chemical class 0.000 claims description 22
- 239000000049 pigment Substances 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 230000007704 transition Effects 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004530 micro-emulsion Substances 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 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 6
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 6
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 6
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 6
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 6
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 5
- WPKYZIPODULRBM-UHFFFAOYSA-N azane;prop-2-enoic acid Chemical compound N.OC(=O)C=C WPKYZIPODULRBM-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000000700 radioactive tracer Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000012703 microemulsion polymerization Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000002537 cosmetic Substances 0.000 abstract description 9
- 239000000976 ink Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000123 paper Substances 0.000 abstract description 3
- 239000004480 active ingredient Substances 0.000 abstract 2
- 230000009477 glass transition Effects 0.000 abstract 2
- 239000007788 liquid Substances 0.000 description 24
- 239000003921 oil Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 10
- 125000000129 anionic group Chemical group 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 8
- 108090000790 Enzymes Proteins 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000013543 active substance Substances 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000007614 solvation Methods 0.000 description 5
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 235000012222 talc Nutrition 0.000 description 3
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 206010047571 Visual impairment Diseases 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical group CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 150000001261 hydroxy acids Chemical group 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000006101 laboratory sample Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000346 nonvolatile oil Substances 0.000 description 2
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical class CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000011049 pearl Substances 0.000 description 2
- YARNEMCKJLFQHG-UHFFFAOYSA-N prop-1-ene;styrene Chemical compound CC=C.C=CC1=CC=CC=C1 YARNEMCKJLFQHG-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
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- 239000004408 titanium dioxide Substances 0.000 description 2
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- 208000029257 vision disease Diseases 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OTJFQRMIRKXXRS-UHFFFAOYSA-N (hydroxymethylamino)methanol Chemical compound OCNCO OTJFQRMIRKXXRS-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
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- DNLZVNZIAOXDTF-UHFFFAOYSA-N 2-[(dimethylamino)methyl]prop-2-enamide Chemical compound CN(C)CC(=C)C(N)=O DNLZVNZIAOXDTF-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WZISPVCKWGNITO-UHFFFAOYSA-N 4-(diethylamino)-2-methylidenebutanamide Chemical compound CCN(CC)CCC(=C)C(N)=O WZISPVCKWGNITO-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical group NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 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
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
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- 239000011260 aqueous acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940067573 brown iron oxide Drugs 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GDCRSXZBSIRSFR-UHFFFAOYSA-N ethyl prop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)C=C GDCRSXZBSIRSFR-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 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
- 230000007774 longterm Effects 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HBVCJGDADPMZEC-UHFFFAOYSA-N n',n'-diethyl-n-propylprop-2-enehydrazide Chemical compound CCCN(N(CC)CC)C(=O)C=C HBVCJGDADPMZEC-UHFFFAOYSA-N 0.000 description 1
- HKTGZPQHFCONFD-UHFFFAOYSA-N n-[(dimethylamino)methyl]-2-methylprop-2-enamide Chemical compound CN(C)CNC(=O)C(C)=C HKTGZPQHFCONFD-UHFFFAOYSA-N 0.000 description 1
- NOUPIZNZZWSTBI-UHFFFAOYSA-N n-butyl-n',n'-diethylprop-2-enehydrazide Chemical compound CCCCN(N(CC)CC)C(=O)C=C NOUPIZNZZWSTBI-UHFFFAOYSA-N 0.000 description 1
- CKIBIKFBPKFOQX-UHFFFAOYSA-N n-butyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCCCN(N(C)C)C(=O)C=C CKIBIKFBPKFOQX-UHFFFAOYSA-N 0.000 description 1
- RCLLINSDAJVOHP-UHFFFAOYSA-N n-ethyl-n',n'-dimethylprop-2-enehydrazide Chemical compound CCN(N(C)C)C(=O)C=C RCLLINSDAJVOHP-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 230000001131 transforming effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
Polymeric particles comprising a polymeric matrix that has been formed from a blend of monomers comprising a first monomer which is an ethylenically unsaturated ionic monomer and a second monomer which is an ethylenically unsaturated hydrophobic monomer which is capable of forming a homopolymer of glass transition temperature in excess of 50< DEG >C, wherein secondary particles are distributed throughout the matrix, in which the secondary particles comprise a hydrophobic polymer that has been formed from an ethylenically unsaturated hydrophobic monomer which is capable of forming a homopolymer of glass transition temperature in excess of 50< DEG >C and optionally other monomers, which hydrophobic polymer is different from the polymeric matrix. Also claimed is a process for preparing particles. The particles have improved shatter resistance. Preferably the polymeric particles comprise an active ingredient, especially a colourant. Such particles combine improved shatter resistance with the ability to retain the active ingredient. The particles of the invention can be used in a variety of industrial applications, for instance in the manufacture of inks, paper and cosmetics.
Description
The present invention relates to polymer beads and make their method.The polymer beads that cherishes a special interest comprises especially (entrapped) tinting material of embedding of activeconstituents.
The embedding of activeconstituents can be finished by many methods.In these technology some relate to form the polymerization shell around centronucleus or activeconstituentss.Other method relates to preparation polymeric material matrix, and activeconstituents spreads all over this matrix and distributes.
The capsular method of various preparations has been proposed in the document.For example known, in like this hydrophobic liquid being incapsulated,, reduce the pH value then and produce the opacity aminoplast(ic) resin shell wall that surrounds hydrophobic liquid by hydrophobic liquid being distributed in the aqueous medium that contains the melamine formaldehyde precondensate.Described the variant of these class methods in GB-A-2073132, AU-A-27028/88 and GB-A-1507739, wherein capsule preferably is used to provide the encapsulated ink that is used for the pressure-sensitive noncarbon recording paper.
But though be opacity and durable based on the capsule of melamine formaldehyde resin, they often have the relatively poor shortcoming of opacity at high temperature.The danger of separating out formaldehyde is also arranged in addition.
At for example GB 1,275,712,1,475,229 and 1,507,739, DE 3,545,803 and US3, the routine techniques that forms polymer shell has been described in 591,090.
At US 3,838, in 007, the enzyme droplet that is dispersed in the aqueous solution of gelatin for example is scattered in the water, crosslinked then, contain the cross-linked particles of the gelatin of enzyme with generation.
At EP-A-356, in 240, with enzyme or other biological products be encapsulated into method in the polymeric material matrix be by the mixed polymerization material with comprise the liquid, aqueous of biological products, this mixture is dispersed in the water-immiscible liquid, and makes this dispersion azeotropic.Product can or be the coarse relatively bead that can reclaim, and perhaps is the stabilising dispersions of water-immiscible liquid small particles.
At EP-A-356, the description of various compositions and method is arranged in 239, it mainly expects sealing of the enzyme that is used for liquid or other washing composition.Wherein one type the product of Miao Shuing comprises oil with nuclear, encloses core and the particle that surrounds oil bodying thing shell, and this nuclear comprises the matrix polymer that contains enzyme.
The particle that comprises the matrix polymer of activeconstituents can form the dispersion in the oil, this dispersion can be dispersed in the aqueous solution of sealing polymkeric substance or blend polymer then, and can cause polymer deposition around oil particles then, this oil particles comprises the particle of the matrix polymer that contains activeconstituents.
US 5,744,152 have described the method that forms polymer beads, this polymer beads is introduced with the volatile amine of polymkeric substance as the solution of water-soluble salt, this polymkeric substance is insoluble relatively and non-swelling in acid, activeconstituents disperses or is dissolved in the whole acid, and heats this solution forming butt matter and to make this amine volatilization, and forms the polymkeric substance that is insoluble to acid thus.Can be by regulating the release that the pH value is controlled activeconstituents carefully.Special design this method is used for embedding large-sized relatively component, especially enzyme, fungi, spore, bacterium, cell or microbiotic, and the adjusting by pH discharges these components with suitable releasing mechanism.
WO 97/24178 has described microparticle compositions, it comprises the particle with the polymeric matrix that contains the detergency activeconstituents, wherein polymeric matrix is formed by free alkali (free base) form of cationic polymers, and this cationic polymers is the multipolymer of the amine monomers of unsaturated hydrophobic monomer of ethylenic and the unsaturated replacement of ethylenic.When free alkali monomer and hydrophobic monomer are dissolved in organic solvent, make this free alkali monomer and hydrophobic monomer polymerization,, can prepare matrix granule like this to form the solution of free alkali polymer inorganic solvent.Then add the volatility aqueous acid, wherein solvent has the volatility higher than acid.Thereby distilling off solvent is left the aqueous solution of the salt form of polymkeric substance then.Suitable volatile acid is an acetate, and in this case, suitable solvent is a n-butyl acetate.Activeconstituents is particularly including enzyme, and this enzyme can be released by the medium that dilution comprises them.
All aforesaid reference all are with the embedding of activeconstituents or seal relevantly that this activeconstituents will be released, so do not provide any indication of the permanent embedding that how to obtain material, the undersized especially relatively thing class of this material in the step of back.
Known have to provide seal or the various technology of the tinting material of embedding.
WO 91/06277 has described cosmetic formulations, and this preparaton has activable hiding (dormant) pigment that is dispersed in anhydrous alkali or the carrier.Make the pigment or the liquid carrier dispersion micro encapsulation that ground, the powder of stable to form, dry, free-pouring micro-sized particle.Preferred encapsulating method is by cohesion, for example by making liquid dispersion at the droplet of continuous, outside aqueous phase emulsification with the formation micro-dimension, and the mixture that adds colloidal materials by this way to the outside in mutually, to form above the droplet or on every side precipitation, form outside wall or shell thus at each.When standing physical force, microcapsule tend to break and discharge the pigment of hiding.
US5234711 relates to the useful method that granules of pigments is sealed in making cosmetic product.The purpose of the disclosure is to use the vinyl polymerization encapsulating method to be used to increase wetting properties, dispersibility and the thermotolerance of granules of pigments.This encapsulating method comprises redox or the free radical vinyl polymerization in the aqueous medium.
EP 225799 has described the solid non magnetic colorant materials of liquid, gel, wax shape or the watery fusion solid-state carrier micro encapsulation in mutually, and it is encapsulated in the polymerization shell.Being absorbed on the shell is silane or titanate coupling agent, and it increases the lipophilicity on solid colorant materials surface.
US3876603 relates to the method for encapsulated pigments, and it comprises makes the polymerization in the dispersion liquid of aliphatic solvents of at least a ethylenically unsaturated monomers.This carries out in the presence of the strong solvent of polymerization single polymerization monomer.This method is used the imines of the polymerizable ethylene linkage formula unsaturated acid of about 0.2～about 6 weight %, about 0.2～about 6 weight %, the dispersion stabilizer of about 1～about 40 weight %, and this dispersion stabilizer comprises the multipolymer of the branching that contains two polymeric segment.One section by the dispersion liquid solvation, and second section is anchor formula (anchor) polymkeric substance with first section opposed polarity, relatively not by the dispersion liquid solvation, and can with the polymer beads grappling of ethylenically unsaturated monomers.This anchor formula polymkeric substance comprise can with the ethylenically unsaturated monomers copolymerization to form false dispersive side group.
EP 455342 relates to make-up composition, and it comprises by making the solvation dyestuff be attached in the resin and mixing the pigment that forms with cosmetics carrier.The amount of pigment that exists is enough to provide the pigment of attractive amount, and this amount is enough to provide attractive dressing effect when using on skin, nail or hair.Can use the acceptable soluble dye of any cosmetic.Can use any resin, as long as it can be ground into fine powder.Can like this solvation dyestuff be attached in the resin: the solvation dyestuff is joined in plastifying or the fused resin; Perhaps dyestuff is dissolved in the solution of not polymer resin and dyestuff and resin mutual solvent, then this resin of polymerization; Dyestuff is contacted with resin.Think that the toner of dye-impregnated is used for various make-up compositions.
An object of the present invention is to provide polymer beads, it comprises the activeconstituents of the embedding that can keep for a long time under various conditions.The particularly advantageous product that comprises tinting material embedding or that seal that provides, this product are chronically and keep this tinting material when standing different environment.For pigment, oil soluble and water-soluble dye also is like this, wherein is difficult to for good and all keep them usually.In make-up composition, if dyestuff or pigment can not forever keep, this can damage the long-term visual effect of makeup.
WO 02/090445 has proposed this problem, and polymer beads is provided, and it comprises polymeric matrix and spreads all over its dispersive tinting material.This polymeric matrix is formed by monomeric blend, this grams of monomer blend is included as first monomer of the unsaturated ion monomer of ethylenic, it is the salt of volatility counter ion, with second monomer that is the unsaturated hydrophobic monomer of ethylenic, described second monomer forms the homopolymer that second-order transition temperature surpasses 50 ℃.Conventional matrix polymer comprises the multipolymer that has been formed by vinylbenzene and ammonium acrylate.Polymer beads has demonstrated extraordinary maintain property, and can keep tinting material under various conditions.But these particles often have shortcoming, and promptly they may break even be broken when being handled roughly under certain conditions, and this can cause the loss of tinting material.
Another object of the present invention provides anti-fragmentation and can stand the particle of rough processing.A concrete aspect relates to provides anti-broken (shatter resistance) particle, and it comprises activeconstituents, especially tinting material.
US4056653 has described the spheroidal particle with 10～100 microns median sizes, and wherein the surface is covered by the about 0.1 micron semisphere piece of diameter.Particle is formed by the multipolymer of alhpa olefin with 3～8 carbon atoms and α β ethylenic unsaturated carboxylic acid, and wherein multipolymer has the hydroxy-acid group up to 90%, and this hydroxy-acid group is neutralized by metal ion and is ionized.Particle forms free flowing powder, and this powder is used to prepare the anti-broken coating of transparency protected property of glass.
The polymkeric substance of tinting material that the purpose of this invention is to provide embedding, wherein particle is not broken, even and tinting material after life-time service, also can not filter (leach out).On the one hand, expectation provides dye solution is embedded into method in the polymer beads that is attached in the cosmetic formulations, and wherein dyestuff keeps for good and all by embedding, and is not released before using, in the application process or after using.
In addition tinting material seal or the embedding meeting causes the visual impairment of tinting material.This may be owing to due to the light of polymkeric substance absorption specific wavelength, perhaps be because due to the irregular form of polymer beads sometimes.Also be like this when particle is not crush resistance.Crack in the particle or disruptive particle also will cause the visual impairment of tinting material.
The particle of the crush resistance with raising that can be used for various application need be provided.Particularly, need provide the product that comprises tinting material embedding or that seal, this product keeps tinting material for a long time, and demonstrates the crush resistance of raising when standing different environment.When using pigment, oil soluble and water-soluble dye, also be like this.
In addition, the purpose of this invention is to provide selectable method oil soluble or water-soluble dye are converted into the product that can be used as pigment in various application.
Therefore, another object of the present invention provides the polymkeric substance of the tinting material that comprises embedding, and it produces the visual effect that improves.
Another purpose of the present invention provides the particle that combines following feature: keeping tinting material, is crush resistance under rough condition, also demonstrates good visual performance.
Therefore, according to the present invention, we provide polymer beads, it comprises the polymeric matrix that has been formed by grams of monomer blend, this grams of monomer blend is included as first monomer of the unsaturated ion monomer of ethylenic, with second monomer that is the unsaturated hydrophobic monomer of ethylenic, described second monomer forms the homopolymer that second-order transition temperature surpasses 50 ℃
Wherein secondary particle spreads all over the matrix distribution, wherein secondary particle comprises the hydrophobic polymer that has been formed by the unsaturated hydrophobic monomer of ethylenic and other optional monomer, the unsaturated hydrophobic monomer of this ethylenic can form the homopolymer that second-order transition temperature surpasses 50 ℃, and this hydrophobic polymer is different with polymeric matrix
In another aspect of this invention, we provide the method for preparing polymer beads, and this polymer beads comprises polymeric matrix and the secondary particle that spreads all over the matrix distribution,
Wherein polymeric matrix is formed by monomeric blend, this grams of monomer blend is included as first monomer of the unsaturated ion monomer of ethylenic, with second monomer that is the unsaturated hydrophobic monomer of ethylenic, described second monomer forms the homopolymer that second-order transition temperature surpasses 50 ℃
Wherein, secondary particle comprises the hydrophobic polymer that has been formed by the unsaturated hydrophobic monomer of ethylenic and other optional monomer, the unsaturated hydrophobic monomer of this ethylenic can form the homopolymer that second-order transition temperature surpasses 50 ℃, and this hydrophobic polymer is different with polymeric matrix
This method may further comprise the steps:
A) provide the water of polymer salt, this polymer salt is by comprising that the first and second monomeric grams of monomer blend form,
B) form secondary particle at aqueous phase, perhaps secondary particle combined with water,
C) be formed on the immiscible liquid phase of water in comprise the dispersion of water, its preferably include the amphiphilic polymerization stabilizer with form emulsion and
D) make the dispersion dehydration, wherein water evaporates from aqueous particulate, forms the solid particulate that comprises the secondary particle that spreads all over the matrix polymer distribution thus.
Particle according to a first aspect of the invention and have the crush resistance of raising by the product that the method according to second aspect present invention obtains.
First monomer that is used to form polymeric matrix is preferably the salt of volatility counter ion component.In the process of dehydrating step (D), the volatility counter ion component of expectation evaporation salt.In other words, evaporation at least a portion counter ion component.For example when polymeric matrix is ammonium salt, volatile constituent ammonia will be evaporated.Therefore, in the distillation stage, matrix polymer will be converted into its free acid or free alkali form.
Desirably, particle of the present invention can comprise activeconstituents, for example UV absorption agent, UV tamper, fire retardant, reactive dyestuffs tracer material.Polymer beads preferably includes tinting material.Tinting material can be selected from pigment, dyestuff or color lake (lake).In this particulate process of preparation, especially expect activeconstituents for example tinting material be dissolved in or be scattered in aqueous phase, distribute thereby activeconstituents (for example tinting material) can spread all over whole matrix polymer.Have been found that polymer beads of the present invention demonstrates the crush resistance of raising and the visual performance of improvement, even and under life-time service, the activeconstituents that this polymeric matrix does not allow any embedding yet for example tinting material is released.Especially expectation provides particle, and wherein activeconstituents, especially tinting material spread all over whole polymeric matrix distribution, and polymeric matrix should be impermeable for activeconstituents (for example tinting material).
If make polymeric matrix crosslinked, polymerization product can further be strengthened.This crosslinked can be owing to comprising in present method due to the cross-linking step.This can realize by comprise the self-crosslinking group in polymkeric substance, for example have the monomeric repeating unit of methylol functional group.But preferably realize crosslinked by in the aqueous polymerization thing, comprising linking agent.Linking agent normally with polymer chain on the compound of functional group reactions.For example when polymer chain comprised anionic group, suitable crosslinking agent can be aziridine (aziridine), diepoxides, carbon diamide (carbodiamide), silane or polyvalent metal, for example aluminium, zinc or zirconium.Especially preferred a kind of linking agent is ammonium zirconium carbonate or zinc oxide.Another kind of especially preferred linking agent is included in the compound that forms covalent linkage between the polymer chain, for example silane or diepoxides.
Desirably, in dehydrating step, carry out cross-linking process.Therefore, when comprising linking agent, it keeps hiding usually, up to beginning dehydration.
Have been found that, the polymkeric substance that is formed by the specific combination of hydrophobic monomer is aspect tinting material or other active substance opacity, demonstrate sizable improved performance, this hydrophobic monomer can form the homopolymer that second-order transition temperature surpasses 50 ℃, is preferably greater than 60 or 80 ℃.Hydrophobic monomer is meant that solubleness in water is less than the monomer of 5g/100ml water.
The second-order transition temperature of polymkeric substance (Tg) is at Encycopedia of Chemical Technology, the 19th volume, the 4th edition, be defined as this temperature in the 891st page, curl and launch (uncoiling) and all freeze in that 40～50 carbon atoms of the transient motion of this (1) below temperature whole molecule and (2) chain are pulsating.Therefore at it below Tg, polymkeric substance can not demonstrate and flow or caoutchouc elasticity.Can use dsc (DSC) to measure the Tg of polymkeric substance.Therefore according to the linear temperature program, respectively but heat reference sample and the laboratory sample of known Tg concurrently.Two well heaters remain on two samples under the equal temperature.Supervision offers two well heaters realizing the power of this purpose, and the function of the difference between them as the reference temperature drawn, and it is converted into the record of concrete heat as the function of temperature.When reference temperature raises or reduce, and laboratory sample is neither endothermic nor exothermic according to conversion when transforming, and keeps the required heat of temperature will be bigger or still less.The figure of typical expression second-order transition temperature as shown in Figure 1.
Usually, the particulate median size is less than about 100 microns.Frequently, median size is often littler, and for example less than 70 or 80 microns, often less than 40 or 50 microns, typically, median size is 750nm～40 micron.Median size is preferably 10～40 microns, often is 10～30 microns.According to the standard step of document complete documentation, determine mean particle size by the Coulter particle-size analyzer.
Be not limited to theory, think that the particular combinations of ion monomer and described hydrophobic monomer provides the wetting ability and the hardness of appropriate degree to polymkeric substance, the reason that this seemingly improves the opacity of tinting material or other active substance.The existence that comprises the secondary particle of hydrophobic polymer provides the reason of the crush resistance of raising seemingly for particle of the present invention.
Usually can comprise the hydrophobic monomer of at least 50 weight % for the grams of monomer blend for preparing matrix polymer, residuum is made up of ion monomer or potential ionic polymer.One or more anionic monomers or one or more cationic monomers can be used as ion monomer.Also can use the blend of positively charged ion and anionic monomer.Usually the amount of hydrophobic monomer is at least 60 weight %.Preferred compositions comprises the hydrophobic polymer of 65～90 weight %, and for example about 70 or 75%.
The object lesson of described hydrophobic monomer comprises vinylbenzene, methyl methacrylate, methacrylic tert-butyl acrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate.
Have been found that and can not replace hydrophobic monomer with the ethylenically-unsaturated carboxylic acid ester, the ethylenically-unsaturated carboxylic acid ester can not form the homopolymer with at least 50 ℃ of second-order transition temperatures, and does not increase the perviousness of polymkeric substance nocuously.Also preferred Tg should be at least 60 ℃ or even at least 80 ℃.For example use other (methyl) acrylate for example 2-EHA replace hydrophobic monomer of the present invention, be inappropriate.Best result obtains by the monomer that uses the polymkeric substance that can form very high Tg usually.Therefore, use ethyl propenoate or propyl acrylate will produce relatively poor preferred product as hydrophobic monomer.
Ion monomer can comprise negatively charged ion or cation group, or selectively can be the potential ion, for example the form of acid anhydrides.Preferably, ion monomer is unsaturated negatively charged ion of ethylenic or potential anionic monomer.Suitable negatively charged ion or potential anionic monomer comprise vinylformic acid, methacrylic acid, ethylacrylic acid (ethacrylic acid), fumaric acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, Ba Dousuan, vinylacetic acid, (methyl) allyl sulphonic acid, vinyl sulfonic acid and 2-acrylamido-2-methyl propane sulfonic acid.The preferred anionic surfactants monomer is carboxylic acid or acid anhydrides.
When ion monomer is a negatively charged ion for example during the carboxylic acid or anhydride, the volatility counter ion can be ammonia or volatile amine component.Usually the volatile amine component will be for can be at low temperature to moderate temperature, for example up to evaporated liquid under 200 ℃ the temperature.Preferably, can be under reduced pressure be lower than this volatile amine of evaporation under 100 ℃ the temperature.Can free sour form produce polymkeric substance thus, with the aqueous solution neutralization of ammonium hydroxide or volatile amine, this volatile amine is thanomin, carbinolamine, 1-Propanolamine, 2-Propanolamine, dimethanolamine and diethanolamine for example then.Selectively, can be by ammonium or volatility amine salt and this polymkeric substance of the incompatible preparation of hydrophobic monomer copolymerization that makes anionic monomer.
Usually, can prepare matrix polymer by any suitable polymerization process.For example can prepare this polymkeric substance easily, as described in EP-A-697423 or US-A-5070136 by aqueous emulsion polymerization.This polymkeric substance then can neutralize by the aqueous solution that adds ammonium hydroxide or volatile amine.
In common polymerization process, the blend emulsification that makes hydrophobic monomer and anionic monomer is to the aqueous phase that comprises the appropriate amount emulsifying agent.Usually emulsifying agent can be the emulsifying agent that any commerce is obtainable, be suitable for forming water miscible liquid.Desirably, these emulsifying agents often at aqueous phase than immiscible more easily molten in mutually at monomer and water, thereby often demonstrate high hydrophilic-lipophilic balance (HLB).Available known emulsifying technology carries out monomeric emulsification, and known emulsifying technology comprises makes monomers/water stand vigorous stirring or shearing mutually, or selectively monomers/water was communicated screen cloth or mesh.Then can be by using suitable initiator system, for example UV initiator or thermal initiator carry out polymerization.The technology of suitable initiated polymerization will improve the temperature of monomeric water miscible liquid to being higher than 70 or 80 ℃, add the ammonium persulphate of 50～1000ppm then, in monomeric weight.
Usually, matrix polymer has the molecular weight (use industry standard parameters, measure by GPC) up to 200,000.Polymkeric substance preferably has the molecular weight less than 50,000, and for example 2,000～20,000.Usually the optimum molecular weight of matrix polymer is about 6,000～12,000.
Especially preferred matrix polymer is the multipolymer of vinylbenzene and ammonium acrylate.More preferably, when this process application linking agent, use this polymkeric substance, linking agent is ammonium zirconium carbonate or zinc oxide especially.
In the selectable modification of the inventive method, ion monomer can be positively charged ion or potential positively charged ion, for example ethylenic unsaturated amine.In this form of the present invention, volatility counter ion component is the volatile acid component.Therefore in this form of the present invention, can form matrix polymer with mode like the aforementioned anionic substrates polymer class, different is to replace anionic monomer with positively charged ion or potential cationic monomer.Usually, when polymkeric substance prepares with the multipolymer form of free amine and hydrophobic monomer, by comprising suitable volatile acid, for example acetate, formic acid, propionic acid, butyric acid or or even carbonic acid it is neutralized.Preferably use in the volatile carboxylic acid and polymkeric substance.
Suitable positively charged ion or potential cationic monomer comprise (methyl) propenoic acid dialkyl aminoalkyl ester, (methyl) acryloyl dialkyl aminoalkyl amine or allyl amine and other ethylenic unsaturated amine and their acid salt.Usually, (methyl) propenoic acid dialkyl aminoalkyl ester comprises vinylformic acid dimethylamino methyl esters, dimethylaminoethyl acrylate methyl base amino methyl, the vinylformic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate, vinylformic acid diethylamino ethyl ester, diethyl aminoethyl methacrylate, vinylformic acid dimethylamino propyl ester, the amino propyl ester of dimethylaminoethyl acrylate methyl base, vinylformic acid diethylamino propyl ester, methacrylic acid diethylamino propyl ester, vinylformic acid dimethylamino butyl ester, the amino butyl ester of dimethylaminoethyl acrylate methyl base, vinylformic acid diethylamino butyl ester and methacrylic acid diethylamino butyl ester.Usually dialkyl aminoalkyl (methyl) acrylamide comprises the dimethylaminomethyl acrylamide, the dimethylaminomethyl Methacrylamide, the dimethyl aminoethyl acrylamide, the dimethyl aminoethyl Methacrylamide, the diethylamino ethyl acrylamide, diethylamino ethyl-methyl acrylamide, the dimethylaminopropyl acrylamide, the dimethylaminopropyl Methacrylamide, diethylamino propyl group acrylamide, diethylamino propyl methyl acid amides, dimethylamino butyl acrylamide, dimethylamino butyl methyl acrylamide, diethylamino butyl acrylamide and diethylamino butyl methyl acrylamide.Usually, allyl amine comprises diallyl amine and triallylamine.
Secondary particle comprises the hydrophobic polymer that has been formed by the unsaturated hydrophobic monomer of ethylenic and other optional monomer, the unsaturated hydrophobic monomer of this ethylenic can form the homopolymer that second-order transition temperature surpasses 50 ℃, and this hydrophobic polymer is different with polymeric matrix.The unsaturated hydrophobic monomer of ethylenic can be above about the defined any monomer of second monomer that is used to form matrix polymer.It is identical with second monomer that is used to form polymeric matrix that hydrophobic monomer is preferably.The object lesson of described hydrophobic monomer comprises vinylbenzene, methyl methacrylate, methacrylic tert-butyl acrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate.Hydrophobic monomer is preferably vinylbenzene.
Hydrophobic monomer can be independent polymeric, or selectively can with other hydrophobic monomer polymerization that defines more than one or more.Can comprise other monomer, they are not to form the hydrophobic monomer that second-order transition temperature surpasses 50 ℃ homopolymer, and condition is that this monomer does not bring any harmful effect.Other monomer can be hydrophobic monomer, for example acrylic or methacrylic acid than long-chain alkyl groups, as 2-EHA or stearyl acrylate ester.Usually, when comprising this monomer, their amount should be not more than 20 weight %, based on be used for secondary particle total monomer weight.These monomeric amounts are more preferably less than 5 weight % preferably less than 10 weight %.
Selectively, other monomer can be hydrophilic monomer.Hydrophilic monomer can be non-ionic, as acrylamide, or can be ionic, as defined about first monomer that is used to form matrix polymer.Usually, this monomer often uses with less ratio, thereby polymkeric substance is hydrophobic.When comprising this monomer, their amount should be not more than 20 weight %, based on be used for secondary particle total monomer weight.These monomeric amounts are more preferably less than 5 weight % preferably less than 10 weight %.
Especially preferably, secondary particle comprises the hydrophobic polymer that has fully been formed by the unsaturated hydrophobic monomer of one or more ethylenic, and this hydrophobic monomer can form the homopolymer that second-order transition temperature surpasses 50 ℃.Especially suitable hydrophobic polymer is the multipolymer and the cinnamic homopolymer of vinylbenzene and methyl methacrylate.Vinylbenzene and Polymerization of Methyl thing generally include the vinylbenzene of at least 40 weight % and the methyl methacrylate of 60 weight % at the most.Multipolymer preferably had 50: 50～95: 5, and more preferably 60: 40～80: 20, especially preferred 70: 30～75: 25 vinylbenzene and the weight ratio of methyl methacrylate.
Usually, secondary particle has less than 1 micron, frequent mean particle size less than 750nm.Secondary particle preferably has the mean particle size of 50～500nm scope.Can prepare secondary particle by any conventional means.Usually, can prepare this particle by the aqueous emulsion polymerization.Preferably, according to any typical microemulsion polymerization method that writes down in the prior art, for example described in EP-A-531005 or EP-A-449450, prepare this particle by the aqueous microemulsions polymerization.
Usually, can comprise continuous water (20～80 weight %) by formation, comprise that the microemulsion of monomeric dispersion oil phase (10～30 weight %) and tensio-active agent and/or stablizer (10～70 weight %) prepares secondary particle.Usually tensio-active agent and/or stablizer mainly are present in aqueous phase.Preferred surfactants and/or stablizer are the aqueous solution that is used to form the polymkeric substance of polymeric matrix.Especially preferred tensio-active agent/stablizer is ammonium acrylate and cinnamic multipolymer, defines about matrix polymer as above.
Can be by suitable initiator system, for example UV initiator or thermal initiator cause monomeric polymerization in the microemulsion.The technology of suitable initiated polymerization for example improves the temperature of monomeric water miscible liquid to being higher than 70 or 80 ℃, adds for example Diisopropyl azodicarboxylate of the ammonium persulphate of 50～1000ppm or azo-compound then, in monomeric weight.Selectively, can use for example self-vulcanizing superoxide of suitable superoxide, or light trigger.Can preferably under about room temperature, for example carry out polymerization with light trigger.
Usually, secondary particle comprises having up to 2,000, the polymkeric substance of 000 molecular weight (use industry standard parameters, measure by GPC).Polymkeric substance preferably has the molecular weight less than 500,000, and for example 5,000～300,000.Usually, the optimum molecular weight of polymeric secondary particle is 100,000～200,000.
Preferably, secondary particle has core-shell configuration, and its center comprises the hydrophobic polymer that is aggregated the shell encirclement.More preferably, secondary particle comprises nuclear that comprises hydrophobic polymer and the shell that comprises matrix polymer.Especially preferably, around the nuclear of hydrophobic polymer and in the polymeric process, form the shell of matrix polymer.
As noted earlier, particle of the present invention can comprise activeconstituents, for example UV absorption agent, UV tamper, fire retardant, reactive dyestuffs tracer material or preferred tinting material.
Particle can comprise one or more tinting materials, and tinting material can be any tinting material, for example dyestuff, pigment or color lake.Normally suitable tinting material comprises any organic or inorganic pigment or tinting material, and it is used for makeup, for example pigment that is used for cosmetic formulations of color lake, ferric oxide, titanium dioxide, iron sulphide or other routine by CTFA and FDA approval.The example of pigment comprises mineral dye for example carbon black, D﹠amp; C Red7, calcium color lake, D﹠amp; C Red30, talcum color lake (talc lake), D﹠amp; C Red6, barium color lake, sorrel ferric oxide (Russet iron oxide), Zh 1, brown iron oxide, talcum, kaolin, mica, mica titanium, red iron oxide, Magnesium Silicate q-agent and titanium oxide; With pigment dyestuff for example Red No 202, Red No 204, Red No 205, Red No 206, Red No 219, Red No 228, Red No 404, Yellow No 205, Yellow No 401, Orange No 401 and Blue No 404.The example of oil-soluble colourant comprises Red No 505, Red No 501, Red No225, Yellow No 404, Yellow No 405, Yellow No 204, Orange No 403, BlueNo 403, Green No 202 and Purple No 201.The example of vat dyes (vat dyes) is Red No226, Blue No 204 and Blue No 201.The example of lake dyes comprises various acid dyes with aluminium, calcium or precipitated barium.Also can use conventional dyestuff, it can be oil soluble or water miscible.Be used for suitable dye of the present invention and comprise FD﹠amp; C Blue No 11, FD﹠amp; C Blue No 12, FD﹠amp; C GreenNo 13, FD﹠amp; C Red No 13, FD﹠amp; C Red No 140, FD﹠amp; C Yellow No.15, FD﹠amp; CYellow No.16, D﹠amp; C Blue No.14, D﹠amp; C Blue No.19, D﹠amp; C Green No.15, D﹠amp; C Green No.16, D﹠amp; C Green No.18, D﹠amp; C Orange No.14, D﹠amp; C Orange No.15, D﹠amp; C Orange No.110, D﹠amp; C Orange No.111, D﹠amp; C Orange No.117, FD﹠amp; CRed No.14, D﹠amp; C Red No.16, D﹠amp; C Red No.17, D﹠amp; C Red No.18, D﹠amp; C RedNo.19, D﹠amp; C Red No.117, D﹠amp; C Red No.119, D﹠amp; C Red No.121, D﹠amp; C RedNo.122, D﹠amp; C Red No.127, D﹠amp; C Red No.128, D﹠amp; C Red No.130, D﹠amp; C RedNo.131, D﹠amp; C Red No.134, D﹠amp; C Red No.139, FD﹠amp; C Red No.140, D﹠amp; CViolet No.12, D﹠amp; C Yellow No.17, Ext.D﹠amp; C Yellow No.17, D﹠amp; C Yellow No.18, D﹠amp; C Yellow No.111, D﹠amp; C Brown No.11, Ext.D﹠amp; C Violet No.12, D﹠amp; CBlue No.16 and D﹠amp; C Yellow No.110.This dyestuff is well-known, commercial obtainable material, for example at 21 C.F.R.Part 74 (revision on April 1st, 1988) and the Cosmetics, Toiletry and Fragrancy Association, Inc. the CTFA Cosmetic IngredientHandbook of Chu Baning has described their chemical structure in (1988).These publications are incorporated herein by reference herein.
Tinting material can be the colorant materials of hiding, coupler for example, and it is exposed to, and suitable trigger mechanism for example heats or show color when shining.The coupler of this embedding can be coated in the suitable substrate suitably or be attached in the suitable substrate, handle it then to manifest color.Being provided as toner is that they are can be easier processed and be attached in the substrate in the mode of expectation as the advantage of polymer beads.Although coupler is encapsulated in the polymer beads, it still can be activated.
Method of the present invention comprises that the matrix polymer aqueous solution that will comprise secondary particle is distributed in the water-immiscible liquid.
In the presence of the aqueous solution of for example foregoing matrix polymer, with water miscible liquid and water microemulsion polymeric mode, be used in the monomer polymerization that forms secondary particle, the result can make secondary particle be included in the aqueous solution of matrix polymer.Selectively, can prepare secondary particle separately, be dispersed in then in the aqueous solution of matrix polymer to form dispersion.To anhydrate in order removing from the matrix polymer aqueous solution then, dispersion can be dewatered, the result forms particle of the present invention.
Can be by activeconstituents being distributed in the aqueous solution of matrix polymer, preparing the particle of the present invention that comprises activeconstituents (for example tinting material).Therefore this dispersion will comprise and spread all over activeconstituents (for example tinting material) and the secondary particle that whole matrix polymer distributes.
Usually, water-immiscible liquid is the blend of organic liquid or organic liquid.Preferred organic liquid is the mixture of non-volatility paraffin oil and volatility paraffin oil.Part by weight that can be identical uses two kinds of oil, but preferably usually uses excessive fixed oil, for example greater than the fixed oil and 25 of 50～75 weight parts～less than the ethereal oil of 50 weight parts.
According to obtaining in the particulate method of the present invention, for the present invention, be desirably in and comprise the polymeric amphiphilic stablizer in the water-immiscible liquid.The amphiphilic stablizer can be the obtainable amphiphilic stablizer of any commerce, for example HYPERMER (RTM) (can obtain from ICI).Suitable stabilizers also comprises the stablizer of describing among the WO-A-97/24179.Though except the amphiphilic stablizer, can comprise other stabilization material, as tensio-active agent, but preferred usually, unique stabilization material is the amphiphilic stablizer.
In the method for the invention, dehydrating step can be finished by any means easily.Desirably, can finish dehydration by the dispersion in the oil is carried out vacuum distilling.Usually, this needs high temperature, for example 30 ℃ or higher temperature.Though can use for example 80～90 ℃ of much higher temperature, preferred usually the use is lower than 60 or 70 ℃ temperature.
Preferably replace vacuum distilling to finish dehydration with spraying drying.Suitably, this can finish by the spray drying process described in the WO-A-97/34945.
Dehydrating step is removed from the aqueous solution of matrix polymer and is anhydrated and volatility counter ion component, obtain insoluble and non-swelling dry polymeric matrix in water, wherein comprise and spread all over secondary particle and the optional activeconstituents (for example tinting material) that polymeric matrix distributes.
Particle of the present invention can be used for various industrial application, for example ink, paper and personal-care supplies, for example manufacturing of make-up composition and other personal care formulations.
Following examples are to explanation of the present invention.
Embodiment 1
Be prepared as follows anti-broken yellow microballon, it comprises the pigment of 60 weight % and the crosslinked matrix polymer of 40 weight %:
Be prepared as follows water: comprise 32 weight % styrene-methylmethacrylate copolymers (70/30 weight % monomer ratio with the dilution of 790g water, molecular weight is 200,000) 448g 46% polymer micro-emulsion of microemulsion, this microemulsion is with styrene-propene acid copolymer (the 65/35 weight % monomer ratio of 14 weight %, molecular weight is 6000) stabilization, under super mixer, mill then 313g Yellow#10 Al color lake powder (ex-Kingfisher) and 56g titanium dioxide.The ammonium zirconium carbonate aqueous solution that in the aqueous pigment dispersions of gained, adds 19g 50%.
Individually, prepare oil phase by amphiphilic stablizer (Sipacril 2739OF of 90 weight % methacrylic acid stearyl esters, 10 weight %, molecular weight 40,000) with 1800g Isopar G solvent (can obtain) dilution 76g 20% from Exxon Mobil.Under the high-shear homogenizer above water is joined in this oil phase, having average water droplet particle diameter with formation is 20 microns water-in-oil emulsion.The emulsion that forms is transferred to the 1 liter of reactor that is provided for vacuum distilling.Heating emulsion to 60 ℃ is carried out vacuum distilling then and is anhydrated/Isopar G solvent mixture to remove.Proceed to be atmospherically distilled to 100 ℃, in distillate, do not collect other water.Then, reactor content was kept 1 hour again, to finish the crosslinking reaction between zirconium crosslink agent and the carboxylic acidifying support resin.
After this heat treatment step, reactor content is cooled to 25 ℃, by filtering to isolate coloured microballon of formation, and at 90 ℃ of following oven dryings.The finished product are that to have median size be 20 microns free-pouring yellow microballon.
Embodiment 2
To prepare red microballon with embodiment 1 described identical mode, different is to use 313g Red#7 Ca color lake powder (ex-Kingfisher) to replace Yellow#10 Al color lake powder.
Embodiment 3
To prepare blue microballon with the described identical mode of EXAMPLE l, different is to use 313gBlue#1 Al color lake powder (ex-Kingfisher) to replace Yellow#10 Al color lake powder.
Embodiment 4
This embodiment illustrates the crush resistance of the coloured microballon that is obtained by the present invention.The yellow microballon of the 30g of embodiment 1 is joined in the 270g Isopropyl myristate.The microballon slurry of gained is heated to 75 ℃, uses high-shear mixer with 6 then, 000rmp was with its homogenize 30 minutes.This is cooled to room temperature with blend, and checks microballon under light microscope after handling.Fig. 2 shows coloured particle constructed in accordance.
Embodiment 5
By preparing water with 100g water dilution 200g 46% polymer micro-emulsion (with the styrene-methylmethacrylate copolymer microemulsion of styrene-propene acid copolymer stabilization).Under high-shear mixer, wherein disperse 31g Blue#1 Al color lake powder (ex-Kingfisher) to this.In the dispersion of gained, add the slurry that comprises 20g aqua oxidation zinc and 80g water.
Individually, prepare oil phase by amphiphilic stablizer (forming) by methacrylic acid stearyl ester (90wt%)-methacrylic acid (10wt%) multipolymer with 600g Isopar G (ex Exxon Mobil) dilution 44g 20%.
Down water is distributed in the oil phase the auxiliary of high-shear homogenizer, having average particulate diameter with formation is 20 microns water-in-oil emulsion.This emulsion is transferred to one group of installation is used for the distillatory device.Heating emulsion to 50 ℃, and carry out vacuum distilling and heating (100 ℃ of top temperatures), in distillate, do not collect till the more water.After this, reactor content is kept 1 hour to finish crosslinking reaction again at about 100 ℃.In case after this step is finished, reactant is cooled to 25 ℃, and filters to reclaim coloured pearl.At last, at 90 ℃ of following oven drying pearls, be 20 microns free-pouring blue powder to obtain having median size.
Claims (35)
1. polymer beads, it comprises the polymeric matrix that has been formed by monomeric blend, this grams of monomer blend is included as first monomer of the ethylenic salt unsaturated carboxylic acid of volatility counter ion component, wherein said volatility counter ion component is ammonia or volatile amine, with for being selected from down second monomer of the unsaturated hydrophobic monomer of organizing of ethylenic: vinylbenzene, methyl methacrylate, the methacrylic tert-butyl acrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate, described second monomer forms the homopolymer that second-order transition temperature surpasses 50 ℃
Wherein, secondary particle spreads all over whole matrix and distributes, wherein secondary particle comprises the hydrophobic polymer that has been formed by the unsaturated hydrophobic monomer of ethylenic and other optional monomer, the unsaturated hydrophobic monomer of described ethylenic is selected from down group: vinylbenzene, methyl methacrylate, the methacrylic tert-butyl acrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate, the unsaturated hydrophobic monomer of this ethylenic can form the homopolymer that second-order transition temperature surpasses 50 ℃, described other monomer is selected from down group: 2-EHA or stearyl acrylate ester, this hydrophobic polymer is different with polymeric matrix.
2. according to the polymer beads of claim 1, it comprises activeconstituents.
3. according to the polymer beads of claim 2, it comprises the activeconstituents that is selected from UV absorption agent, UV tamper, fire retardant and reactive dyestuffs tracer material.
4. according to the polymer beads of claim 1, wherein polymeric matrix comprises the polymkeric substance of free acid or free alkali form.
5. according to the polymer beads of claim 1, wherein polymeric matrix is crosslinked.
6. according to the polymer beads of claim 1, wherein polymer beads has the mean particle size less than 100 microns.
7. according to the polymer beads of claim 6, wherein polymer beads has the mean particle size less than 50 microns.
8. according to the polymer beads of claim 1, wherein matrix polymer is the multipolymer of vinylbenzene and ammonium acrylate, and ammonium zirconium carbonate or zinc oxide are as linking agent.
9. according to the polymer beads of claim 1, wherein first monomer is the unsaturated amine salt of ethylenic of volatility counter ion component, and wherein volatility counter ion component is a volatile carboxylic acid.
10. according to the polymer beads of claim 1, wherein secondary particle is formed by vinylbenzene and methyl methacrylate.
11. according to the polymer beads of claim 1, wherein secondary particle has the mean particle size less than 750nm.
12. according to the polymer beads of claim 11, wherein secondary particle has the mean particle size of 50～500nm.
13. according to the polymer beads of claim 1, wherein secondary particle has core-shell configuration, its center comprises hydrophobic polymer, and shell comprises matrix polymer.
14. according to the polymer beads of claim 2, wherein matrix polymer is impervious for activeconstituents.
15. prepare the method for polymer beads, this polymer beads comprises polymeric matrix and the secondary particle that spreads all over whole matrix distribution,
Wherein polymeric matrix is formed by monomeric blend, this grams of monomer blend is included as first monomer of the ethylenic salt unsaturated carboxylic acid of volatility counter ion component, wherein said volatility counter ion component is ammonia or volatile amine, with for being selected from down second monomer of the unsaturated hydrophobic monomer of organizing of ethylenic: vinylbenzene, methyl methacrylate, the methacrylic tert-butyl acrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate, described second monomer forms the homopolymer that second-order transition temperature surpasses 50 ℃
Wherein, secondary particle comprises the hydrophobic polymer that has been formed by the unsaturated hydrophobic monomer of ethylenic and other optional monomer, the unsaturated hydrophobic monomer of described ethylenic is selected from down group: vinylbenzene, methyl methacrylate, the methacrylic tert-butyl acrylate, phenyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate, the unsaturated hydrophobic monomer of this ethylenic can form the homopolymer that second-order transition temperature surpasses 50 ℃, described other monomer is selected from down group: 2-EHA or stearyl acrylate ester, this hydrophobic polymer is different with polymeric matrix
This method may further comprise the steps:
A) provide the water of polymer salt, this polymer salt is by comprising that the first and second monomeric grams of monomer blend form,
B) form secondary particle at aqueous phase, perhaps secondary particle combined with water,
C) be formed on the immiscible liquid phase of water in comprise the dispersion of water, it comprise the amphiphilic polymerization stabilizer with form emulsion and
D) make the dispersion dehydration, wherein water evaporates from aqueous particulate, forms the solid particulate that comprises the secondary particle that spreads all over the matrix polymer distribution thus.
16. according to the method for claim 15, wherein particle comprises activeconstituents.
17. according to the method for claim 16, wherein particle comprises the activeconstituents that is selected from tinting material.
18. according to the method for claim 15, wherein polymeric matrix comprises the polymkeric substance of free acid or free alkali form.
19. according to the method for claim 15, wherein linking agent is included in aqueous phase, and takes place crosslinked at dehydrating step mesostroma polymkeric substance.
20. according to the method for claim 15, wherein the mean particle size of polymer beads is less than 100 microns.
21. according to the method for claim 20, wherein the mean particle size of polymer beads is less than 50 microns.
22. according to the method for claim 15, wherein polymeric matrix is the multipolymer of vinylbenzene and ammonium acrylate, ammonium zirconium carbonate or zinc oxide are as linking agent.
23. according to the method for claim 15, wherein first monomer is the ethylenic unsaturated amine, and volatility counter ion component is a volatile carboxylic acid.
24. according to the method for claim 15, wherein secondary particle is formed by hydrophobic monomer, this hydrophobic monomer is identical with second monomer that is used to form polymeric matrix.
25. according to the method for claim 24, wherein secondary particle is formed by vinylbenzene and methyl methacrylate.
26. according to the method for claim 15, wherein secondary particle has the mean particle size less than 750nm.
27. according to the method for claim 26, wherein secondary particle has the mean particle size of 50～500nm.
28., wherein make particle form the microemulsion of aqueous phase by micro-emulsion polymerization according to the method for claim 15.
29. according to the method for claim 15, wherein secondary particle has core-shell configuration, its center comprises hydrophobic polymer, and shell comprises matrix polymer.
30. according to the method for claim 16, wherein matrix polymer is impervious to activeconstituents.
31. according to the method for claim 17, wherein tinting material is a dyestuff.
32. according to the method for claim 17, wherein dehydrating step comprises vacuum distilling.
33. according to the method for claim 15, wherein dehydrating step comprises spraying drying.
34. according to the method for claim 17, wherein tinting material is a pigment.
35. according to the method for claim 17, wherein tinting material is the color lake.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| GB0413338A GB0413338D0 (en) | 2004-06-15 | 2004-06-15 | Polymeric particles |
| GB0413338.5 | 2004-06-15 | ||
| GB0417073.4 | 2004-07-30 | ||
| GB0417073A GB0417073D0 (en) | 2004-07-30 | 2004-07-30 | Polymeric particles |
| PCT/EP2005/005917 WO2005123796A1 (en) | 2004-06-15 | 2005-06-02 | Polymeric particles |
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| CN1989162A CN1989162A (en) | 2007-06-27 |
| CN1989162B true CN1989162B (en) | 2010-09-08 |
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| CN102015843B (en) * | 2008-05-09 | 2014-02-12 | 巴斯夫欧洲公司 | Polymer encapsulated colourants by spray drying |
| RU2015144080A (en) * | 2013-03-15 | 2017-04-24 | Басф Се | Cross-linked products obtained by ionic crosslinking of a solid brand oligomer and polymer using an ionic crosslinking agent and methods for their preparation |
| AU2014230909B2 (en) | 2013-03-15 | 2018-03-01 | Basf Se | Compositions comprising a copolymer of a solid grade oligomer and a hydrophobic monomer and/or a gas-phase monomer and methods of making the same |
| CN106470946A (en) * | 2014-07-04 | 2017-03-01 | 陶氏环球技术有限责任公司 | There is the inorganic particulate of improvement mobility |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4592990A (en) * | 1982-12-29 | 1986-06-03 | Canon Kabushiki Kaisha | Process for producing toner |
| EP0334126A2 (en) * | 1988-03-21 | 1989-09-27 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Polymeric particles, preparation by colloidally stabilized suspension process, encapsulated toner particles containing them. |
| US5306743A (en) * | 1988-12-24 | 1994-04-26 | Rohm Gmbh | Multiple phase synthetic resin dispersion |
| WO2002090445A1 (en) * | 2001-05-04 | 2002-11-14 | Ciba Specialty Chemicals Water Treatments Limited | Colourants encapsulated in a polymer matrix |
-
2004
- 2004-06-15 GB GB0413338A patent/GB0413338D0/en not_active Ceased
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2005
- 2005-06-02 CN CN200580024497XA patent/CN1989162B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4592990A (en) * | 1982-12-29 | 1986-06-03 | Canon Kabushiki Kaisha | Process for producing toner |
| EP0334126A2 (en) * | 1988-03-21 | 1989-09-27 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Polymeric particles, preparation by colloidally stabilized suspension process, encapsulated toner particles containing them. |
| US5306743A (en) * | 1988-12-24 | 1994-04-26 | Rohm Gmbh | Multiple phase synthetic resin dispersion |
| WO2002090445A1 (en) * | 2001-05-04 | 2002-11-14 | Ciba Specialty Chemicals Water Treatments Limited | Colourants encapsulated in a polymer matrix |
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