EP1451284A1 - Method for producing coated bleach activator granules - Google Patents
Method for producing coated bleach activator granulesInfo
- Publication number
- EP1451284A1 EP1451284A1 EP02804191A EP02804191A EP1451284A1 EP 1451284 A1 EP1451284 A1 EP 1451284A1 EP 02804191 A EP02804191 A EP 02804191A EP 02804191 A EP02804191 A EP 02804191A EP 1451284 A1 EP1451284 A1 EP 1451284A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- formula
- sulfate
- range
- acid
- 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
- 239000008187 granular material Substances 0.000 title claims abstract description 35
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 14
- 239000012190 activator Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 28
- -1 alkali metal phosphonate Chemical class 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003599 detergent Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012459 cleaning agent Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 5
- 229940071118 cumenesulfonate Drugs 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 4
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- ZZXDRXVIRVJQBT-UHFFFAOYSA-M Xylenesulfonate Chemical compound CC1=CC=CC(S([O-])(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-M 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229940070765 laurate Drugs 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229940071104 xylenesulfonate Drugs 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 150000008052 alkyl sulfonates Chemical class 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 abstract description 3
- 238000007596 consolidation process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 239000012876 carrier material Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005728 strengthening Methods 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GHDBLWVVUWTQCG-UHFFFAOYSA-N acetonitrile;n,n-dimethylmethanamine Chemical compound CC#N.CN(C)C GHDBLWVVUWTQCG-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QECVIPBZOPUTRD-UHFFFAOYSA-N N=S(=O)=O Chemical class N=S(=O)=O QECVIPBZOPUTRD-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005011 alkyl ether group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000007931 coated granule Substances 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940079842 sodium cumenesulfonate Drugs 0.000 description 1
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
- C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
- C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
Definitions
- the invention relates to a process for coating bleach activator-containing granules by treatment with an acidic aqueous strengthening solution which contains polymeric polycarboxylate and / or alkali metal phosphonate as the coating and strengthening active ingredient, with simultaneous drying in a fluidized bed apparatus.
- detergents and cleaning agents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents and cleaning agents generally contain other ingredients, which can be summarized under the term washing aids and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents and dye transfer inhibitors. Such auxiliaries also include substances that support the surfactant performance through the oxidative degradation of soiling on the textile or such in the fleet. The same applies analogously to cleaning agents for hard surfaces. Inorganic peroxygen compounds, in particular hydrogen peroxide and solid peroxygen compounds which dissolve in water with the liberation of hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
- oxidation effect of these substances in dilute solutions depends strongly on the temperature; For example, with H 2 O 2 or sodium perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 60 ° C. At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by the addition of so-called bleach activators, for which numerous suggestions, especially from the classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylgly oluril , N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular Sodium non
- European patent application EP 0 464 880 discloses bleach-boosting cationic nitriles of the general formula R'R “R '" N + -CR 1 R 2 -CN X " , in which Ri and R 2 are hydrogen or a substituent with at least one C- Atom, R 'is a C 1-24 - alkyl, alkenyl or alkyl ether group or a group -CR ⁇ R 2 -CN, and R "and R" are each a C 1-24 - alkyl or hydroxyalkyl group and the counter anion X " is an organic sulfonate, an organic sulfate or a carboxylate.
- the international patent application WO 00/50556 discloses the production of solid preparations, which contain cationic nitrile and solid carrier material, by means of a valcuum steam drying process in a mixer.
- the object of the invention was to provide a process which makes it possible to granulate, which contain a cationic nitrile, in particulate washing and cleaning agent to incorporate that the cationic nitrile suffers as far as possible no loss of bleach-activating effect even after storage. It has now been found that the preparation of preparations which meet this requirement is possible by means of a swirl chicite coating process. In this way, a protective coating can be applied to the granules in a simple manner, without having to accept a decrease in the bleach activating effect.
- the invention relates to the production of a coated particulate preparation containing a compound of the formula (I), R 1
- R 3 in the R 1 represents -H, -CH 3 , a C 2-2 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br , -OH, -NH 2 , -CN, an alkyl or alkenylaryl radical with a C ⁇ .2 4 -alkyl group, or for a substituted alkyl or alkenylaryl radical with a C 1-24 alkyl group and at least one further substituent on the aromatic ring
- R and R are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 - CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 - OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -
- the anions X " include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C 1- 0 -alkyl sulfate, C.
- halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, hydrogen carbonate, sulfate, hydrogen sulfate, C 1- 0 -alkyl sulfate, C.
- o-alkyl sulfonate optionally C 1-18 alkyl substituted aryl sulfonate, chlorate, perchlorate and / or the anions of C 1-24 carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures.
- X chloride, sulfate, hydrogen sulfate, ethosulfate, C 12/18 -, C 12/16 - or C 13/15 alkyl sulfate, lauryl sulfate, dodecyl benzene sulfonate, toluenesulfonate, cumene sulfonate, xylene sulfonate or Toluene sulfonate or cumene sulfonate is understood to mean the anion of the ortho-, meta- or /> ⁇ ra isomer of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof. ⁇ r -Isopropylbenzenesulfonic acid is particularly preferred.
- the compound according to general formula I can be packaged in solid form as such or in particulate form, that is to say applied to an organic and / or inorganic carrier material, can be used as starting material in the coating process according to the invention.
- the compound of the formula (I) can be applied to the support material in such a way that the support material is stirred into a solution of the compound of the formula I, as is obtained in the course of its preparation, and the aqueous solvent, if appropriate, in vacuo, if desired at elevated Temperature, subtracts.
- the solution of the compound of the formula I can also be sprayed onto the support material and, if appropriate, or subsequently, subjected to a drying process.
- Enveloping the bleach activator granules produced in accordance with the methods disclosed in German patent applications DE 19740 668 or DE 197 40 671 is also possible by means of the method according to the invention and represents a preferred embodiment of the method according to the invention. It is preferred if the particles resulting from the packaging process have one Have diameters in the range of 0.4 mm to 3 mm.
- Suitable carrier materials are all substances which do not interact in an unacceptably negative way with the compound of the formula I, for example alkali metal sulfonate, surfactants, organic acids and polymers, alkali metal carbonates, alkali metal sulfates, alkali metal hydrogen sulfates,
- Support materials are preferably used whose inner surface is in the range from 10 m 2 / g to 500 m 2 / g, in particular 100 m Ig to 450 m 2 / g.
- the silicate carrier materials which are particularly suitable in the context of the present invention include, for example, both alkali silicates and also silicas, silica gels and clays and mixtures thereof. However, the carrier material is preferably free of zeolites.
- silicate-containing carrier material optionally contains further particulate inert constituents which do not unreasonably impair the stability of the compounds of the formula I.
- Silicas which have been produced by a thermal process can be used as well as silicas produced by wet processes.
- Silica gels are colloidal silicas with elastic to firm consistency and a largely loose pore structure, which results in a high fluid absorption capacity. They can be made by the action of mineral acids on water glass become.
- Clays are naturally occurring crystalline or amorphous silicates of aluminum, iron, magnesium, calcium, potassium and sodium, for example kaolin, talc, pyrophyllite, attapulgite, sepiolite, montmorillionite and bauxite.
- the use of aluminum silicate as a carrier material or as a component of a carrier material mixture is also possible.
- the carrier material preferably has particle sizes in the range from 100 ⁇ m to 1.5 mm.
- steps a) preparation of an aqueous solution containing cationic nitrile, preferably in amounts of 10% by weight to 90% by weight, in particular 15% by weight, are first carried out % to 50% by weight, and optionally alkali metal sulfonate, in particular sodium cumene sulfonate, b) optionally adjusting the solution to an acidic pH, in particular by adding sulfuric acid and / or citric acid c) spraying and drying the solution in a fluidized bed apparatus, d) optionally powdering the primary granules thus obtained using silica, zeolite and / or alkali metal sulfonate, in particular Na-cumene sulfonate, in the fluidized bed, and the optionally powdered granules obtained in this way with the aqueous strengthening and coating solution with simultaneous drying in the same or, if appropriate, one sprayed downstream second fluidized bed apparatus.
- the granules can then be discharged from the fluidized bed apparatus and, if necessary, separated into good and coarse / fine particles, in particular by sieving. If appropriate, the return of fine grain and / or ground coarse grain to the fluidized bed in step c) and / or the return of fine grain and / or ground coarse grain to the powdering step d) can follow.
- the coated bleach activator granules obtainable by the process according to the invention or the proportion of good grains thereon preferably have average particle diameters in the range from 0.2 mm to 2.5 mm, in particular in the range from 0.4 mm to 2.0 mm.
- Its bulk density is preferably in the range from 300 g / 1 to 1000 g / 1, in particular in the range from 400 g / 1 to 800 g / 1.
- the proportion of compound of the formula (I) is preferably in the range from 10% by weight to 90% by weight, in particular from 15% by weight to 50% by weight. It is preferably used for the production of particulate detergents or cleaning agents.
- Fluidized bed devices which can be used in a method according to the invention are known, for example, from European Patent EP 0 603 207 B1 or German Patent Application DE 197 50 424.
- the through openings can be covered by a grid, in particular with mesh sizes of less than 600 ⁇ m.
- the grid can be arranged inside or above the passage openings. However, the grid is preferably located directly below the passage openings of the inflow floor, as is known in principle from German patent application DE 197 50 424.
- a metal gauze with the appropriate mesh size can be sintered onto the underside of a known inflow floor or attached in some other way.
- the metal gauze preferably consists of the same material as the inflow floor, in particular of stainless steel.
- the fine-meshed grid prevents particles from falling through, especially when the system stops unscheduled, but also especially in the case of particularly heavy particles with bulk densities of around 1000 g / l, even during operation.
- the mesh size of said grid is preferably between 200 and 400 ⁇ m. It is also advantageous if the inflow floor used has a pressure loss of at most 10 mbar and in particular at most 6 mbar.
- the aqueous strengthening and coating solution is applied in a fluidized bed apparatus.
- Suitable solidifying agents and coating agents are polymeric polycarboxylates, in particular polymerization products of acrylic acid, methacrylic acid or maleic acid, or copolymers of at least two of these, which can be used in completely or partially neutralized form, in particular in the form of the alkali metal salts.
- polymeric polycarboxylate phosphonic acid or alkali metal phosphonate can be used.
- sodium is the preferred alkali metal in each case.
- the setting of the solution is preferably as low as possible Viscosity for good droplet distribution when spraying into the fluidized bed while drying.
- the pH of the solution is not from the outset in the acidic range, by adding acids compatible with the system, in particular by adding sulfuric acid and / or citric acid, it is brought to acidic values, in particular to values in the pH range from 4 to 4.4 , set. It is preferred that, based on the granules to be coated, so much of the aqueous solution is sprayed on that the coating makes up 1% by weight to 25% by weight, in particular 2% by weight to 15% by weight.
- the granules can then be discharged from the fluidized bed in a manner known in principle and, if appropriate, massaged according to the particle size, wherein, as stated above, undesirably small particles (fine particles) and undesirably large particles (coarse particles) can optionally be returned to a granulation process after a grinding step.
- the classified good grain can be introduced again into a fluidized-bed apparatus and sprayed onto the hardening and coating solution in order to further improve the product properties of the granulate if necessary.
- a granulate encased by the process according to the invention is stable in storage, has good free-flowing properties and is sufficiently stable to be able to be mixed in a customary manner with other particulate constituents of washing or cleaning agents.
- Coated granules obtainable by the process according to the invention are used in particular particulate washing or cleaning agents, preferably in amounts such that these agents have contents of 0.1% by weight to 10% by weight, in particular 0.2% by weight. up to 7% by weight of bleach activator according to formula (I).
- a supply air temperature of 95 ° C and an exhaust air temperature of 55 ° C from a homogeneous aqueous solution of trimethylammonium acetonitrile methosulfate and Na-cumolsulfonate (mass ratio 1: 1, dry matter content 30%) with a throughput of the solution of 3 kg / h within 5 h, a granulate which was still very sticky.
- the stickiness could be eliminated by repeated granulation with a 20% aqueous solution of polymeric polycarboxylate (Sokalan® CP45, manufacturer BASF) under the same conditions with regard to the supply air flow, supply air temperature and exhaust air temperature.
- the polymer content in the granules thus obtained was 5% by weight.
- the grain size of the granules was in the range from 0.4 mm to 2.0 mm, the bulk density was 700 g / 1.
- the granules were then sieved and the portion with particle sizes of between 0.8 and 1.6 mm was mixed with the other detergent components of a detergent formulation. The finished detergent could be used without clumping.
- the granules obtained according to Example 2 were again introduced into the fluidized bed apparatus and sprayed from the side with the 20% polymer solution already used at 130 ° C. supply air temperature and 65 ° C. exhaust air, so that a 20 percent by weight coating was produced.
- the granules obtained according to Example 3 were again introduced into the fluidized bed apparatus and sprinkled with the 20% polymer solution from the side at 130 ° C. supply air temperature and 65 ° C. exhaust air, so that a 10 percent by weight coating was produced.
- Example 2 In a fluidized bed apparatus with a diameter of 15 cm (Glatt® AGT 1800), granules containing trimethylammonium acetonitrile methosulfate were sprayed with the polymer solution used in Example 1 using two-component nozzles arranged below.
- the supply air volume was 100 m 3 / h, the supply air temperature was 120 ° C and the exhaust air temperature 60 ° C.
- the two-component nozzles were operated with warm air at 75 ° C; the air factor of the nozzles was 1.5 (kg air / kg solution).
- the coating layer on the finished granulate was 10% by weight. A complete coating layer was visible under the milcroscope.
- the granules obtained consisted of
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10159388A DE10159388A1 (en) | 2001-12-04 | 2001-12-04 | Process for the production of coated bleach activator granules |
DE10159388 | 2001-12-04 | ||
PCT/EP2002/013127 WO2003048290A1 (en) | 2001-12-04 | 2002-11-22 | Method for producing coated bleach activator granules |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1451284A1 true EP1451284A1 (en) | 2004-09-01 |
EP1451284B1 EP1451284B1 (en) | 2006-05-03 |
Family
ID=7707896
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02804191A Expired - Lifetime EP1451284B1 (en) | 2001-12-04 | 2002-11-22 | Method for producing coated bleach activator granules |
Country Status (8)
Country | Link |
---|---|
US (1) | US20040248754A1 (en) |
EP (1) | EP1451284B1 (en) |
JP (1) | JP2005514467A (en) |
AT (1) | ATE325182T1 (en) |
AU (1) | AU2002365628A1 (en) |
DE (2) | DE10159388A1 (en) |
ES (1) | ES2260519T3 (en) |
WO (1) | WO2003048290A1 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10314441A1 (en) * | 2003-03-31 | 2004-10-21 | Henkel Kgaa | Bleach activator compounds |
DE102004012568A1 (en) * | 2004-03-12 | 2005-12-08 | Henkel Kgaa | Bleach activators and process for their preparation |
DE102016015660A1 (en) * | 2016-12-31 | 2018-07-05 | Weylchem Wiesbaden Gmbh | Granules, their use and detergents and cleaning agents containing them |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4127323A1 (en) * | 1991-08-20 | 1993-02-25 | Henkel Kgaa | METHOD FOR PRODUCING TENSIDE GRANULES |
WO1994003395A1 (en) * | 1992-08-01 | 1994-02-17 | The Procter & Gamble Company | Peroxyacid bleach precursor compositions |
US5888419A (en) * | 1995-06-07 | 1999-03-30 | The Clorox Company | Granular N-alkyl ammonium acetontrile compositions |
US5814242A (en) * | 1995-06-07 | 1998-09-29 | The Clorox Company | Mixed peroxygen activator compositions |
US6235218B1 (en) * | 1995-06-07 | 2001-05-22 | The Clorox Company | Process for preparing N-alkyl ammonium acetonitrile compounds |
US6183665B1 (en) * | 1995-06-07 | 2001-02-06 | The Clorox Company | Granular N-alkyl ammonium acetonitrile compositions |
DE19649375A1 (en) * | 1996-11-29 | 1998-06-04 | Henkel Kgaa | Acetonitrile derivatives as bleach activators in detergents |
DE19740668A1 (en) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Storage-stable bleach activator granulate obtained using acid-modified layered silicate as binder |
DE19740671A1 (en) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Bleach activator granulate containing ammonium nitrile and layered silicate |
DE19740669A1 (en) * | 1997-09-16 | 1999-03-18 | Clariant Gmbh | Coated ammonium nitrile bleach activator granules used in e.g. detergents |
DE19750424A1 (en) * | 1997-11-14 | 1999-05-20 | Henkel Kgaa | Production of detergent granules with high bulk density |
DE19841184A1 (en) * | 1998-09-09 | 2000-03-16 | Clariant Gmbh | bleach activator |
JP2002532615A (en) * | 1998-12-15 | 2002-10-02 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン | Acetonitrile derivatives as bleach activators |
DE19908051A1 (en) * | 1999-02-25 | 2000-08-31 | Henkel Kgaa | Process for the preparation of compounded acetonitrile derivatives |
DE10038086A1 (en) * | 2000-08-04 | 2002-02-14 | Clariant Gmbh | Process for the preparation of hydrolysis-stable ammonium nitriles |
DE10038832A1 (en) * | 2000-08-04 | 2002-03-28 | Henkel Kgaa | Coated bleach activators |
US20030166484A1 (en) * | 2000-09-28 | 2003-09-04 | Kingma Arend Jouke | Coated, granular n-alkylammonium acetonitrile salts and use thereof as bleach activators |
DE10049237A1 (en) * | 2000-09-28 | 2002-04-11 | Basf Ag | Coated, granular N-alkylammonium acetonitrile salts and their use as a bleach activator |
DE10057045A1 (en) * | 2000-11-17 | 2002-05-23 | Clariant Gmbh | Particulate bleach activators based on acetonitriles |
DE10159386A1 (en) * | 2001-12-04 | 2003-06-12 | Henkel Kgaa | Process for the production of bleach activator granules |
-
2001
- 2001-12-04 DE DE10159388A patent/DE10159388A1/en not_active Ceased
-
2002
- 2002-11-22 WO PCT/EP2002/013127 patent/WO2003048290A1/en active IP Right Grant
- 2002-11-22 ES ES02804191T patent/ES2260519T3/en not_active Expired - Lifetime
- 2002-11-22 JP JP2003549470A patent/JP2005514467A/en not_active Withdrawn
- 2002-11-22 AU AU2002365628A patent/AU2002365628A1/en not_active Abandoned
- 2002-11-22 AT AT02804191T patent/ATE325182T1/en not_active IP Right Cessation
- 2002-11-22 DE DE50206700T patent/DE50206700D1/en not_active Expired - Fee Related
- 2002-11-22 EP EP02804191A patent/EP1451284B1/en not_active Expired - Lifetime
-
2004
- 2004-06-04 US US10/861,188 patent/US20040248754A1/en not_active Abandoned
Non-Patent Citations (1)
Title |
---|
See references of WO03048290A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE10159388A1 (en) | 2003-06-12 |
ATE325182T1 (en) | 2006-06-15 |
WO2003048290A1 (en) | 2003-06-12 |
AU2002365628A1 (en) | 2003-06-17 |
EP1451284B1 (en) | 2006-05-03 |
ES2260519T3 (en) | 2006-11-01 |
US20040248754A1 (en) | 2004-12-09 |
DE50206700D1 (en) | 2006-06-08 |
JP2005514467A (en) | 2005-05-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1017773B1 (en) | Bleaching activators based on ammonium nitrile in the form of coated granules | |
EP1017776B1 (en) | Bleaching activators in the form of granules | |
EP1421169B1 (en) | Encapsulated active ingredient preparation for use in particulate detergents and cleaning agents | |
EP1913124B1 (en) | Method for the production of bleaching catalyst granules | |
DE3012922A1 (en) | Bleach and detergent | |
EP1305386B1 (en) | Enclosed bleach activators | |
EP1319705B1 (en) | Bleach activator cogranulates | |
EP0985728B1 (en) | Bleach activator granulate | |
DE102016015660A1 (en) | Granules, their use and detergents and cleaning agents containing them | |
EP1207195A2 (en) | Particulate bleach activators comprising acetonitril | |
DE4040654A1 (en) | GRANULES WITH COVERED BLEACH ACTIVATOR | |
EP1451284B1 (en) | Method for producing coated bleach activator granules | |
EP1309542B1 (en) | Method for producing hydrolysis-stable ammonium nitriles | |
DE69303900T2 (en) | RE-RELEASABLE COVERED ACTIVE SUBSTRATES | |
EP1451283B1 (en) | Method for producing bleach activator granules | |
DE10038180A1 (en) | Use of a novel bleach activator compound in dishwashing detergent compositions | |
AT387401B (en) | Bleach and detergent | |
WO2004096756A1 (en) | Method for producing granulated ammonium nitrile | |
EP1163318A1 (en) | Anionic surface active granulates | |
EP1111035A2 (en) | Combination of active agents for incorporation in detergent compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20040526 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR |
|
AX | Request for extension of the european patent |
Extension state: RO SI |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20060503 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060503 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060503 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060503 Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060503 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060503 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 50206700 Country of ref document: DE Date of ref document: 20060608 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060803 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060803 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20060829 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20061003 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2260519 Country of ref document: ES Kind code of ref document: T3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061130 Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061130 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061130 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061130 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20070206 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 20061130 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20071115 Year of fee payment: 6 Ref country code: ES Payment date: 20071219 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061122 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20071126 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060804 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20071108 Year of fee payment: 6 Ref country code: GB Payment date: 20071121 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060803 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060503 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061122 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060503 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060503 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20081122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081122 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20090731 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090603 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081122 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20081124 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081124 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20081130 |