CA2375408A1 - Detergent particles and processes for making them - Google Patents
Detergent particles and processes for making them Download PDFInfo
- Publication number
- CA2375408A1 CA2375408A1 CA002375408A CA2375408A CA2375408A1 CA 2375408 A1 CA2375408 A1 CA 2375408A1 CA 002375408 A CA002375408 A CA 002375408A CA 2375408 A CA2375408 A CA 2375408A CA 2375408 A1 CA2375408 A1 CA 2375408A1
- Authority
- CA
- Canada
- Prior art keywords
- detergent
- mixer
- acid
- mean particle
- geometric mean
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 260
- 239000002245 particle Substances 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 51
- 230000008569 process Effects 0.000 title abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 132
- -1 photobleaches Substances 0.000 claims description 90
- 239000007844 bleaching agent Substances 0.000 claims description 61
- 150000001875 compounds Chemical class 0.000 claims description 58
- 102000004190 Enzymes Human genes 0.000 claims description 38
- 108090000790 Enzymes Proteins 0.000 claims description 38
- 239000002304 perfume Substances 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 25
- 238000004061 bleaching Methods 0.000 claims description 13
- 239000002689 soil Substances 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 150000004760 silicates Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 abstract description 45
- 238000012545 processing Methods 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 description 38
- 239000002585 base Substances 0.000 description 37
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 37
- 229940088598 enzyme Drugs 0.000 description 37
- 150000003839 salts Chemical class 0.000 description 34
- 239000002253 acid Substances 0.000 description 33
- 239000002243 precursor Substances 0.000 description 32
- 239000010457 zeolite Substances 0.000 description 30
- 229910021536 Zeolite Inorganic materials 0.000 description 28
- 239000012530 fluid Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 28
- 125000000217 alkyl group Chemical group 0.000 description 27
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 239000011734 sodium Substances 0.000 description 26
- 229910052708 sodium Inorganic materials 0.000 description 25
- 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 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- 239000003795 chemical substances by application Substances 0.000 description 21
- 239000002518 antifoaming agent Substances 0.000 description 19
- 150000004965 peroxy acids Chemical class 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229920001296 polysiloxane Polymers 0.000 description 17
- 229910052783 alkali metal Inorganic materials 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 150000007513 acids Chemical class 0.000 description 13
- 239000012190 activator Substances 0.000 description 13
- 239000000975 dye Substances 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 239000000654 additive Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 239000004367 Lipase Substances 0.000 description 10
- 108090001060 Lipase Proteins 0.000 description 10
- 102000004882 Lipase Human genes 0.000 description 10
- 150000008051 alkyl sulfates Chemical group 0.000 description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 235000019421 lipase Nutrition 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 229920005646 polycarboxylate Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 150000004665 fatty acids Chemical class 0.000 description 8
- 230000004907 flux Effects 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 108010065511 Amylases Proteins 0.000 description 7
- 102000013142 Amylases Human genes 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
- 239000003945 anionic surfactant Substances 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 7
- 229960004106 citric acid Drugs 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229920000620 organic polymer Polymers 0.000 description 7
- 239000000344 soap Substances 0.000 description 7
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 6
- 239000003352 sequestering agent Substances 0.000 description 6
- 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 6
- 238000005406 washing Methods 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 5
- 108091005804 Peptidases Proteins 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 235000019418 amylase Nutrition 0.000 description 5
- 229940025131 amylases Drugs 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 150000004967 organic peroxy acids Chemical class 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 238000005204 segregation Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 4
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 4
- SFHBJXIEBWOOFA-UHFFFAOYSA-N 5-methyl-3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OC(C)COC(=O)C2=CC=C1C=C2 SFHBJXIEBWOOFA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- 230000002366 lipolytic effect Effects 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 230000003381 solubilizing effect Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 3
- 108010059892 Cellulase Proteins 0.000 description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 108010056079 Subtilisins Proteins 0.000 description 3
- 102000005158 Subtilisins Human genes 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- JPZROSNLRWHSQQ-UHFFFAOYSA-N furan-2,5-dione;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1OC(=O)C=C1 JPZROSNLRWHSQQ-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 235000012752 quinoline yellow Nutrition 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 235000019832 sodium triphosphate Nutrition 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 2
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 108091005658 Basic proteases Proteins 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 101100201838 Caenorhabditis elegans rsp-6 gene Proteins 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 108010084185 Cellulases Proteins 0.000 description 2
- 102000005575 Cellulases Human genes 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- 108090000371 Esterases Proteins 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 2
- 150000001204 N-oxides Chemical class 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- 108091005507 Neutral proteases Proteins 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 108700020962 Peroxidase Proteins 0.000 description 2
- 102000003992 Peroxidases Human genes 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 108010059820 Polygalacturonase Proteins 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- 241000589516 Pseudomonas Species 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000003704 aspartic acid Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 108010005774 beta-Galactosidase Proteins 0.000 description 2
- 102000005936 beta-Galactosidase Human genes 0.000 description 2
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 235000012745 brilliant blue FCF Nutrition 0.000 description 2
- 239000004161 brilliant blue FCF Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229940106157 cellulase Drugs 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 108010005400 cutinase Proteins 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 108010093305 exopolygalacturonase Proteins 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 108010020132 microbial serine proteinases Proteins 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003605 opacifier Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004177 patent blue V Substances 0.000 description 2
- 235000012736 patent blue V Nutrition 0.000 description 2
- DMCJFWXGXUEHFD-UHFFFAOYSA-N pentatriacontan-18-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)CCCCCCCCCCCCCCCCC DMCJFWXGXUEHFD-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000004172 quinoline yellow Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 235000012751 sunset yellow FCF Nutrition 0.000 description 2
- 239000004173 sunset yellow FCF Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 108010075550 termamyl Proteins 0.000 description 2
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- UYXFOIMFLBVYDL-UHFFFAOYSA-N 1,2,4,7-tetramethyl-1,4,7-triazonane Chemical compound CC1CN(C)CCN(C)CCN1C UYXFOIMFLBVYDL-UHFFFAOYSA-N 0.000 description 1
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
- WLDGDTPNAKWAIR-UHFFFAOYSA-N 1,4,7-trimethyl-1,4,7-triazonane Chemical compound CN1CCN(C)CCN(C)CC1 WLDGDTPNAKWAIR-UHFFFAOYSA-N 0.000 description 1
- LRPVVAOGGZFVFO-UHFFFAOYSA-N 1,5,9-trimethyl-1,5,9-triazacyclododecane Chemical compound CN1CCCN(C)CCCN(C)CCC1 LRPVVAOGGZFVFO-UHFFFAOYSA-N 0.000 description 1
- GHPCICSQWQDZLM-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-1-methyl-3-propylurea Chemical compound CCCNC(=O)N(C)S(=O)(=O)C1=CC=C(Cl)C=C1 GHPCICSQWQDZLM-UHFFFAOYSA-N 0.000 description 1
- GIVBQSUFWURSOS-UHFFFAOYSA-N 1-ethenyltriazole Chemical compound C=CN1C=CN=N1 GIVBQSUFWURSOS-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- LVVZBNKWTVZSIU-UHFFFAOYSA-N 2-(carboxymethoxy)propanedioic acid Chemical class OC(=O)COC(C(O)=O)C(O)=O LVVZBNKWTVZSIU-UHFFFAOYSA-N 0.000 description 1
- HWQVXNFIYABVIW-UHFFFAOYSA-N 2-(carboxymethylamino)-4,5-dihydroxypentanoic acid Chemical compound OCC(O)CC(C(O)=O)NCC(O)=O HWQVXNFIYABVIW-UHFFFAOYSA-N 0.000 description 1
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 1
- NSMMFSKPGXCMOE-UHFFFAOYSA-N 2-[2-(2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC=C1S(O)(=O)=O NSMMFSKPGXCMOE-UHFFFAOYSA-N 0.000 description 1
- CQWXKASOCUAEOW-UHFFFAOYSA-N 2-[2-(carboxymethoxy)ethoxy]acetic acid Chemical compound OC(=O)COCCOCC(O)=O CQWXKASOCUAEOW-UHFFFAOYSA-N 0.000 description 1
- JKZLOWDYIRTRJZ-UHFFFAOYSA-N 2-[6-(octanoylamino)hexanoyloxy]benzenesulfonic acid Chemical compound CCCCCCCC(=O)NCCCCCC(=O)OC1=CC=CC=C1S(O)(=O)=O JKZLOWDYIRTRJZ-UHFFFAOYSA-N 0.000 description 1
- OARDBPIZDHVTCK-UHFFFAOYSA-N 2-butyloctanoic acid Chemical class CCCCCCC(C(O)=O)CCCC OARDBPIZDHVTCK-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WJZIPMQUKSTHLV-UHFFFAOYSA-N 2-ethyldecanoic acid Chemical class CCCCCCCCC(CC)C(O)=O WJZIPMQUKSTHLV-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NZCIWANIJJJEML-UHFFFAOYSA-N 2-methyl-1,4,7-triazonane Chemical compound CC1CNCCNCCN1 NZCIWANIJJJEML-UHFFFAOYSA-N 0.000 description 1
- PFFITEZSYJIHHR-UHFFFAOYSA-N 2-methyl-undecanoic acid Chemical class CCCCCCCCCC(C)C(O)=O PFFITEZSYJIHHR-UHFFFAOYSA-N 0.000 description 1
- PLVOWOHSFJLXOR-UHFFFAOYSA-N 2-pentylheptanoic acid Chemical class CCCCCC(C(O)=O)CCCCC PLVOWOHSFJLXOR-UHFFFAOYSA-N 0.000 description 1
- APKRDOMMNFBDSG-UHFFFAOYSA-N 2-propylnonanoic acid Chemical class CCCCCCCC(C(O)=O)CCC APKRDOMMNFBDSG-UHFFFAOYSA-N 0.000 description 1
- XHULUQRDNLRXPF-UHFFFAOYSA-N 3-ethenyl-1,3-oxazolidin-2-id-4-one Chemical compound C(=C)N1[CH-]OCC1=O XHULUQRDNLRXPF-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- AFHIIJICYLMCSH-VOTSOKGWSA-N 5-amino-2-[(e)-2-(4-benzamido-2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C(C(=C1)S(O)(=O)=O)=CC=C1NC(=O)C1=CC=CC=C1 AFHIIJICYLMCSH-VOTSOKGWSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N Aspartic acid Chemical class OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RWHAETHMBBUPFN-SSPAHAAFSA-N C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O.O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO Chemical class C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O.O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO RWHAETHMBBUPFN-SSPAHAAFSA-N 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- RTMBGDBBDQKNNZ-UHFFFAOYSA-L C.I. Acid Blue 3 Chemical compound [Ca+2].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=C(O)C=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1.C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=C(O)C=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 RTMBGDBBDQKNNZ-UHFFFAOYSA-L 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 101100148128 Caenorhabditis elegans rsp-4 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- CCPHAMSKHBDMDS-UHFFFAOYSA-N Chetoseminudin B Natural products C=1NC2=CC=CC=C2C=1CC1(SC)NC(=O)C(CO)(SC)N(C)C1=O CCPHAMSKHBDMDS-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- 229910014569 C—OOH Inorganic materials 0.000 description 1
- 108010092681 DNA Primase Proteins 0.000 description 1
- 102000016559 DNA Primase Human genes 0.000 description 1
- 102100036727 Deformed epidermal autoregulatory factor 1 homolog Human genes 0.000 description 1
- 101710172577 Deformed epidermal autoregulatory factor 1 homolog Proteins 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000223198 Humicola Species 0.000 description 1
- 241001373560 Humicola sp. Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical class OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920003091 Methocel™ Polymers 0.000 description 1
- FUVGZDDOHNQZEO-UHFFFAOYSA-N NS(=O)(=O)NCl Chemical compound NS(=O)(=O)NCl FUVGZDDOHNQZEO-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- 101710127332 Protease I Proteins 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- 241000589774 Pseudomonas sp. Species 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OIQPTROHQCGFEF-QIKYXUGXSA-L Sunset Yellow FCF Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-QIKYXUGXSA-L 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 241001285933 Thermomyces sp. Species 0.000 description 1
- 101710137710 Thioesterase 1/protease 1/lysophospholipase L1 Proteins 0.000 description 1
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 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
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000008365 aqueous carrier Substances 0.000 description 1
- 238000010936 aqueous wash Methods 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- SEJPYGHRHLPLII-UHFFFAOYSA-N benzenesulfonyl 6-(nonanoylamino)hexaneperoxoate Chemical compound CCCCCCCCC(=O)NCCCCCC(=O)OOS(=O)(=O)C1=CC=CC=C1 SEJPYGHRHLPLII-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229940055580 brilliant blue fcf Drugs 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical class O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- XNOQNFJEPBFKLL-UHFFFAOYSA-N butanedioic acid;1,2-diaminopropan-2-ol Chemical compound CC(N)(O)CN.OC(=O)CCC(O)=O.OC(=O)CCC(O)=O XNOQNFJEPBFKLL-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 235000012698 chlorophylls and chlorophyllins Nutrition 0.000 description 1
- 239000001752 chlorophylls and chlorophyllins Substances 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000010367 cloning Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000004121 copper complexes of chlorophylls and chlorophyllins Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000001461 cytolytic effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical class ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DUCCPNVOQJMMAN-UHFFFAOYSA-N dimethylamino hexanoate Chemical compound CCCCCC(=O)ON(C)C DUCCPNVOQJMMAN-UHFFFAOYSA-N 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-L diphosphonate(2-) Chemical compound [O-]P(=O)OP([O-])=O XQRLCLUYWUNEEH-UHFFFAOYSA-L 0.000 description 1
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical class O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- XWENCHGJOCJZQO-UHFFFAOYSA-N ethane-1,1,2,2-tetracarboxylic acid Chemical class OC(=O)C(C(O)=O)C(C(O)=O)C(O)=O XWENCHGJOCJZQO-UHFFFAOYSA-N 0.000 description 1
- XZUAPPXGIFNDRA-UHFFFAOYSA-N ethane-1,2-diamine;hydrate Chemical class O.NCCN XZUAPPXGIFNDRA-UHFFFAOYSA-N 0.000 description 1
- IGBSXRIJNMDLFB-UHFFFAOYSA-N ethane-1,2-diamine;pentanedioic acid Chemical compound NCCN.OC(=O)CCCC(O)=O.OC(=O)CCCC(O)=O IGBSXRIJNMDLFB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical class OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical class OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000010412 laundry washing Methods 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 235000014012 manganese gluconate Nutrition 0.000 description 1
- 239000011683 manganese gluconate Substances 0.000 description 1
- 229940072543 manganese gluconate Drugs 0.000 description 1
- OXHQNTSSPHKCPB-IYEMJOQQSA-L manganese(2+);(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Mn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OXHQNTSSPHKCPB-IYEMJOQQSA-L 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical group COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- ARGDYOIRHYLIMT-UHFFFAOYSA-N n,n-dichloro-4-methylbenzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N(Cl)Cl)C=C1 ARGDYOIRHYLIMT-UHFFFAOYSA-N 0.000 description 1
- PJBJJXCZRAHMCK-UHFFFAOYSA-N n,n-dichlorobenzenesulfonamide Chemical compound ClN(Cl)S(=O)(=O)C1=CC=CC=C1 PJBJJXCZRAHMCK-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- RRCSSMRVSNZOFR-UHFFFAOYSA-N phenyl 3,5,5-trimethylhexanoate;sodium Chemical compound [Na].CC(C)(C)CC(C)CC(=O)OC1=CC=CC=C1 RRCSSMRVSNZOFR-UHFFFAOYSA-N 0.000 description 1
- ZRXJXIVOMZDPKQ-UHFFFAOYSA-N phenyl 6-(nonanoylamino)hexanoate Chemical compound CCCCCCCCC(=O)NCCCCCC(=O)OC1=CC=CC=C1 ZRXJXIVOMZDPKQ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- IFIDXBCRSWOUSB-UHFFFAOYSA-N potassium;1,3-dichloro-1,3,5-triazinane-2,4,6-trione Chemical compound [K+].ClN1C(=O)NC(=O)N(Cl)C1=O IFIDXBCRSWOUSB-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- NJKRDXUWFBJCDI-UHFFFAOYSA-N propane-1,1,2,3-tetracarboxylic acid Chemical class OC(=O)CC(C(O)=O)C(C(O)=O)C(O)=O NJKRDXUWFBJCDI-UHFFFAOYSA-N 0.000 description 1
- NJEVMKZODGWUQT-UHFFFAOYSA-N propane-1,1,3,3-tetracarboxylic acid Chemical class OC(=O)C(C(O)=O)CC(C(O)=O)C(O)=O NJEVMKZODGWUQT-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229940071089 sarcosinate Drugs 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 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
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-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
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- PYILKOIEIHHYGD-UHFFFAOYSA-M sodium;1,5-dichloro-4,6-dioxo-1,3,5-triazin-2-olate;dihydrate Chemical compound O.O.[Na+].[O-]C1=NC(=O)N(Cl)C(=O)N1Cl PYILKOIEIHHYGD-UHFFFAOYSA-M 0.000 description 1
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 description 1
- DAPMZWDGZVFZMK-UHFFFAOYSA-N sodium;2-[2-[4-[4-[2-(2-sulfophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonic acid Chemical group [Na].[Na].OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=C(C=2C=CC(C=CC=3C(=CC=CC=3)S(O)(=O)=O)=CC=2)C=C1 DAPMZWDGZVFZMK-UHFFFAOYSA-N 0.000 description 1
- RPQSWSMNPBZEHT-UHFFFAOYSA-M sodium;2-acetyloxybenzenesulfonate Chemical compound [Na+].CC(=O)OC1=CC=CC=C1S([O-])(=O)=O RPQSWSMNPBZEHT-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- KQHKITXZJDOIOD-UHFFFAOYSA-M sodium;3-sulfobenzoate Chemical compound [Na+].OS(=O)(=O)C1=CC=CC(C([O-])=O)=C1 KQHKITXZJDOIOD-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- OYNITBPACPPTCI-UHFFFAOYSA-M sodium;boric acid;hydrogen carbonate Chemical compound [Na+].OB(O)O.OC([O-])=O OYNITBPACPPTCI-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003443 succinic acid derivatives Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004026 tertiary sulfonium compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- VUYXVWGKCKTUMF-UHFFFAOYSA-N tetratriacontaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO VUYXVWGKCKTUMF-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- ASTWEMOBIXQPPV-UHFFFAOYSA-K trisodium;phosphate;dodecahydrate Chemical class O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O ASTWEMOBIXQPPV-UHFFFAOYSA-K 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
- C11D3/50—Perfumes
-
- 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
-
- 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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0063—Photo- activating compounds
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)
- Detergent Compositions (AREA)
Abstract
Particulate detergents and methods for making them with improved process flexibility are disclosed. The detergent particulates are formed from a combination of pre-formed detergent particulates and other detergent ingredients which may also be preformed such as blown powders, extrudates or agglomerates or particulate raw materials. Selection of the feed streams into a low or moderate shear mixing process enable density of the finished detergent particle to be controlled without requiring careful control of the processing conditions.
Description
DETERGENT PARTICLES AI'rD PROCESSES FOR MAKING THEM
Field of the Invention The present invention relates to particulate detergent compositions and an improved process for making such compositions. The detergent compositions of the invention are suitable for anv cleaning process, such as laundry and dishwashing detergent compositions. Such particulate compositions may be used directly in their particulate form or may first be formed into detergent tablets by any standard tabletting process such as compaction.
Background of the Invention In order to meet the needs of the consumer. in addition to providing good cleaning, detergent compositions must meet many additional requirements including good aesthetics, good flow properties, good solubility- and good dispensing performance into wash water. In order to meet all of these requirements, the complexity of detergent compositions and range of products offered has growm. Formulation flexibility for producing such complex compositions is therefore extremely important and many methods for formulating detergent compositions are already known.
In view of the high performance requirements of the consumer, achieving uniform dosage of all of the detergent actives in the composition has increased importance, in particular where sophisticated detergent ingredients present in detergents at low levels make a significant impact on one of the performance features mentioned above. This problem is exacerbated by the advent of "compact" or low dosage granular detergent products. These low dosage detergents are currently in high demand as they conserve resources and can be sold is small packages which are more convenient for consumers prior to use. However, in a low dosage of detergent, where actives are present in very low levels, significant variability may occur in the concentration of such actives in each unit dosage. Performance problems have been identified with some compact detergent products and the present inventors have now found that this may be due to formulation variability where low level detergent ingredients which give a significant impact on one or more of the performance factors mentioned above may vary considerably from dose to dose.
Summary of the Invention The present invention therefore reduces these problems by providing a process in which such low dosage/high impact ingredients can be dispersed uniformly throughout a detergent formulation. Segregation is minimised without the need to incorporate high levels of fillers to form such low dosage/high impact ingredients into larger particles.
Field of the Invention The present invention relates to particulate detergent compositions and an improved process for making such compositions. The detergent compositions of the invention are suitable for anv cleaning process, such as laundry and dishwashing detergent compositions. Such particulate compositions may be used directly in their particulate form or may first be formed into detergent tablets by any standard tabletting process such as compaction.
Background of the Invention In order to meet the needs of the consumer. in addition to providing good cleaning, detergent compositions must meet many additional requirements including good aesthetics, good flow properties, good solubility- and good dispensing performance into wash water. In order to meet all of these requirements, the complexity of detergent compositions and range of products offered has growm. Formulation flexibility for producing such complex compositions is therefore extremely important and many methods for formulating detergent compositions are already known.
In view of the high performance requirements of the consumer, achieving uniform dosage of all of the detergent actives in the composition has increased importance, in particular where sophisticated detergent ingredients present in detergents at low levels make a significant impact on one of the performance features mentioned above. This problem is exacerbated by the advent of "compact" or low dosage granular detergent products. These low dosage detergents are currently in high demand as they conserve resources and can be sold is small packages which are more convenient for consumers prior to use. However, in a low dosage of detergent, where actives are present in very low levels, significant variability may occur in the concentration of such actives in each unit dosage. Performance problems have been identified with some compact detergent products and the present inventors have now found that this may be due to formulation variability where low level detergent ingredients which give a significant impact on one or more of the performance factors mentioned above may vary considerably from dose to dose.
Summary of the Invention The present invention therefore reduces these problems by providing a process in which such low dosage/high impact ingredients can be dispersed uniformly throughout a detergent formulation. Segregation is minimised without the need to incorporate high levels of fillers to form such low dosage/high impact ingredients into larger particles.
In accordance with the present invention there is now provided a method for making a detergent particles comprising selecting detergent base particles having a geometric mean particle diameter from 500 - 2000 microns, in a moderate to low shear mixer adhering detergent active particulates to the detergent base particles, wherein the detergent active particulates have a geometric mean particle diameter no greater than 40% of the geometric mean particle diameter of the detergent base particles and comprise a detergent active selected from perfumes. enzymes, photobleaches, catalysts, soil release polymers, suds suppressors, bleaching compounds, whitening agents and layered silicates.
The present invention also provides detergent panicles produced by such a process, and detergent compositions incorporating these particles.
As used herein, it is intended to mean that a detergent active particulate is bound to the detergent base particulate, the two components subsequently appearing in a detergent composition as an individual detergent particle.
Detailed Description of the Invention Physical Properties The detergent active particulates preferably have a geometric mean particle diameter which is below 200~tm, preferably below 150~m and even below 100 Vim. The geometric mean particle diameter of the detergent active particulates is generally above I
O~tm preferably above 20 ~tm and may even be above 40~m or above 60~m.
As used herein, the phrase "geometric mean particle diameter" means the geometric mass median diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sieving. A
suitable sieving method is in accordance with ISO 3118 (1976). A suitable device is the Ro-Tap testing sieve shaker Model B using 8 inch sieves of selected sizes. As used herein, the phrase "geometric standard deviation" or "span" of a particle size distribution means the geometric breadth of the best-fitted log-normal function to the above-mentioned particle size data which can be accomplished by the ratio of the diameter of the 84.13 percentile divided by the diameter of the 50~' percentile of the cumulative distribution (Dg4_,3/D50)i See Gotoh et al, Powder Technolo~v Handbook, pp. 6-11, Marcel Dekker 1997.
The detergent base particles have a geometric mean particle diameter from 500 to 2000~m. The geometric mean particle diameter of the detergent base particles is generally greater than SSO~m or even greater than 600~m or 650~m. Preferably, the geometric mean particle diameter of the detergent base particles is below 1500~un.
The present invention also provides detergent panicles produced by such a process, and detergent compositions incorporating these particles.
As used herein, it is intended to mean that a detergent active particulate is bound to the detergent base particulate, the two components subsequently appearing in a detergent composition as an individual detergent particle.
Detailed Description of the Invention Physical Properties The detergent active particulates preferably have a geometric mean particle diameter which is below 200~tm, preferably below 150~m and even below 100 Vim. The geometric mean particle diameter of the detergent active particulates is generally above I
O~tm preferably above 20 ~tm and may even be above 40~m or above 60~m.
As used herein, the phrase "geometric mean particle diameter" means the geometric mass median diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sieving. A
suitable sieving method is in accordance with ISO 3118 (1976). A suitable device is the Ro-Tap testing sieve shaker Model B using 8 inch sieves of selected sizes. As used herein, the phrase "geometric standard deviation" or "span" of a particle size distribution means the geometric breadth of the best-fitted log-normal function to the above-mentioned particle size data which can be accomplished by the ratio of the diameter of the 84.13 percentile divided by the diameter of the 50~' percentile of the cumulative distribution (Dg4_,3/D50)i See Gotoh et al, Powder Technolo~v Handbook, pp. 6-11, Marcel Dekker 1997.
The detergent base particles have a geometric mean particle diameter from 500 to 2000~m. The geometric mean particle diameter of the detergent base particles is generally greater than SSO~m or even greater than 600~m or 650~m. Preferably, the geometric mean particle diameter of the detergent base particles is below 1500~un.
The detergent particles produced preferably have a geometric standard deviation of from 1 to about 2, preferably from I .0 to 1. ~, more preferably from about 1.0 to about I .4. Preferred fully formulated detergents comprising the detergent particles also have such a geometric standard deviation.
Preferably the geometric mean particle diameter of the detergent active particulates is no greater than 20% of the geometric mean particle diameter of the detergent base particles more preferably no greater than 10% and may even be below 5% of the geometric mean particle diameter of the detergent base particles. Generally in the detergent particles, no more than 25wrt% is derived from the detergent active particulates, preferably no greater than 10 wt°io. The invention may even be useful where the proportion of the detergent particles derived from the detergent active particulates is no greater than 5 or even no greater than 2 wt%.
As used herein the term "bulk densin-" refers to the uncompressed, untapped powder bulk density, as measured by pouring an excess of particulate sample through a funnel into a smooth metal vessel (e.g. a 500m1 volume cylinder) scraping off the excess off the heap above the rim of the vessel, measuring the remaining mass of powder and dividing the mass by the volume of the vessel.
The bulk density of the detergent particles produced and also of the detergent base particles is generally above 200 g/1 and may be as high as 1500 g/1. It is particularly preferred that the bulk density a finished detergent composition comprising the detergent particles produced according to the present invention is greater than 550 g/1, preferably greater than 600 g/1 or even above 650 g/1. The bulk density of the detergent particles produced is therefore generally from 400g/1 to 1100 g/1, generally above 500g/1 or even above 550 or 650g/1, generally less than 1 OOOg/1 or below 900g/1. The invention may be particularly useful for forming detergent particles having a low bulk density such as below 550 or even below 500 or 450 g/1.
The detergent base particles for use in the method of the present invention may comprise a single detergent ingredient in particulate form or may be a pre-mix of detergent ingredients.
Where the detergent base particles comprise a pre-mix, the separate detergent ingredients may simply be mixed together or may comprise a pre-formed particulate comprising any combination of two or more detergent ingredients, or mixtures thereof, optionally with single detergent ingredients. Suitable pre-formed particulates for the base particles may have been formed by spray-drying, agglomeration, marumerisation, extrusion or compaction, all of which methods for combining detergent ingredients are well-known in the art. Particularly preferred pre-formed particulates are powders obtained from spray-drying processes, agglomerates and extrudates.
Spray-dried powders are particularly useful. Pre-formed particulates made according to at least one low shear mixing step. for example in a fluidised bed. for example by fluid bed agglomeration are particularly preferred. Particularly preferred panicles are as described in our co-pending application filed today under reference number CW2158F.
Suitable spray-drying processes for forming such pre-formed particulates are described for example in EP-A-763594 or EP-A-437888. Suitable processes for forming pre-formed particulates which are agglomerates are described for example in W093/25378, EP-A-367339, EP-..A-420317 or EP-A-506184 and suitable processes for forming pre-formed particulates by extrusion are described for example in W091/02047.
Such pre-formed particulates may be added to the mixer in their wet or dry state. They are preferably added to the mixer in their dry state as addition in their wet state may have an adverse effect on flow into the mixer. Alternatively it may be preferred that the pre-formed particulates are formed in a first stage of a moderate to low shear mixer and the detergent active particulates are added in a second stage so that the pre-formed particulates may be in a wet state when they are contacted with the detergent active particulates. Thus, the pre-formed particulate may be for example an agglomerate, blown powder or extrudate which has not yet undergone a final drying stage.
Generally this means that a solvent used as a binding agent for the processing is present in higher amounts than are desirably present in a finished particulate detergent. Generally the solvent is water and wet particulates will have a free water content for example of froml5 to 30 wt % of the pre-formed particulate. Often, however, the pre-formed particulate will already have undergone a drying step prior to addition to the mixer so that the water content will be below 15 wt %, preferably below 10 wt %. Generally the free water content of the detergent base particles on entry into the mixer will be below 1 S wt %, preferably below 10 wt %.
It may be preferred that the detergent base particles comprise a surfactant or mixture of surfactants. Suitable surfactants are described below. The surfactant content of the detergent base particles or a pre-formed particulate component forming all or part of the detergent base particles is preferably from 5 to 80 % by weight of the particulate component.
Amounts of surfactants above 10 or even above 30% may be preferred. Amounts of surfactant below 70% or even below 50% may be preferred. Where the detergent base pre-formed particulate component comprises surfactant, generally it will in addition comprise a builder or alkalinity agent such as sodium carbonate, zeolite, or phosphate. For example, each of these components individually, or in mixtures may be present in amounts above 5%, preferably above 10°~0 or even above 20% by weight of the content of the pre-formed particulate component. Particularly preferred builder components are sodium carbonate and/or zeolite. Zeolite A and zeolite MAP are both suitable.
The detergent base particles preferably also comprises an organic builder such as a poly carboxylic acid andior salt such as citric acid. tartaric acid. malic acid, succinic acid and their salts or a polymeric polycarboxylate such as polymers based on acrylic acids or malefic acids or co-polymers thereof. Such components are generally present in the particle at levels below 15 wt of the particulate component, preferably below 10 W % of the particulate component.
Other preferred ingredients in the pre-formed particulate component are chelants such as phosphonate chelants NTA, DTPA and succinic acid derivative chelants, as described below.
These components are preferably present in the detergent base particles in amounts below ~ wt or even below 2 wt ° o. Suds supressors andior soil release polymers and/or bleach activators are also preferred ingredients in pre-formed particulates.
Where the particulate components are detergent raw materials, any particulate detergent ingredient is suitable. These may be solid surfactants or soaps. or water soluble or dispersable polymeric materials, enzymes. bleaching components such as bleach activators or bleach salts such as peroxy salts. Highly suitable single ingredients in particulate form include inorganic components, particularly water-soluble inorganic components such as builders and bleach salts such as alkali metal percarbonates and/or perborates. These ingredients are discussed in more detail below .
Suitable detergent ingredients for incorporation either into the detergent particles themselves, or for post-addition to formulate a fully formulated detergent composition are discussed below.
The detergent active particulates are selected from perfumes, enzymes, photobleaches, catalysts, soil release polymers, suds suppressors, bleaching compounds, whitening agents and layered silicates.
Perfumes Preferred detergent active particulates comprise perfume. Any perfume or perfume composition can be used. However, it must be solid or in combination with other components so that it has a solid form. For example it may be loaded onto a particulate carrier such as zeolite, or any other known solid carrier, for example as described in W094/16046, ES93000006, EP-A-535942, and EP-A-294206. More preferably it is present in encapsulated form.
Suitable encapsulates are described for example in W094/12613, EP-A-539025, EP-A-478326, EP-A-383406, EP-A-382464, EP-A-346034, EP-A-70719. Particularly preferred encapsulates comprise starch.
Preferred perfumes contain at least one component with a low molecular weight volatile component, e.g. having a molecular weight of from 150 to 450 or preferably 350. Preferably, the perfume component comprises an oxygen-containing functional group. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.
Enzymes The detergent active particulates may comprise one or more enzymes. Suitable enzymes include the commercially available lipases, cutinases, amylases. neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazvm, and Esperase by Novo Industries A/S
(Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Preferred amylase enzymes may be those described in PCT/ US 9703635, and in W095/26397 and W096/23873. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001%
to 0.5% by weight based on the content in the final detergent composition. The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcalieenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcalieenes, which is described in EP-B-0218272. Another preferred lipase is obtained by cloning the gene from Humicola lanuy'nosa and expressing the gene in Aspereillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414. Huge-Jensen et al, issued March 7, 1989.
Photobleaches Preferred detergent active particulates comprise photobleach particles.
Preferred photo-bleaches herein comprise a compounds having a porphin or porphvrin structure.
Porphin and porphvrin, in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub-class of porphin. The references to porphin in this application will include porphyrin. The porphin structures preferably comprise a metal element or canon, preferably Ca, Mg, P. Ti, Cr, Zr, In. Sn or Hf, more preferably Ge, Si or Ga, or more preferably A1 , most preferably Zn. It can be preferred that the photo-bleach or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pvridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.
The photo-bleaching compound or component can have solubilizing groups as substituents.
Alternatively, or in addition hereto the photo-bleaching agent can comprise a polymeric component capable of solubilizing the photo-bleaching compound, for example PVP, PVNP, PVI
or co-polymers thereof or mixtures thereof.
Highly preferred photo-bleaching compounds have a phthalocyanine structure, which preferably have the metal elements or canons described above. The phthalocyanines can be substituted, suitable examples include the phthalocyanine structures which are substituted at one or more of the l -4, 6. 8-11, 13, 15-18, 20, 22-25, 27 atom positions.
One preferred group of photobleaches comprise a polymeric component and a photobleaching component integrated with one another, whereby the weight ratio of polymeric component to photobleaching component is from 1:1 to 1000:1, preferably 20:1 to 100:1.
Particularly preferred polymeric compounds are formed from monomeric units selected from N-vinylpyrolidone, N-vinylacetamide, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyltriazole, 4-vinylpyridine arid 4-vinylpyrilidine-N-oxide. Preferred photo-bleaching compounds are metals, preferably zinc, phthalocyamines or aluminium. Such photo-bleaches are described in GB
2329397A.
Soil Release Polymers Preferred soil release polymers (SRPs) typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
This can enable stains occurring subsequent to treatment with the SRP to be more easily cleaned in later washing procedures. Preferred SRPs include oligomeric terephthalate esters, typically prepared by _g_ processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one. nvo, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
Suitable SRPs include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P.
Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRPs include the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters ofU.S. 4,711,730. December 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly-(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857. October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRPs useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
SRPs also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the Cl-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SM 100T"' and METOLOSE SM200T"', which are methyl cellulose ethers manufactured by Shin-etsu Kagaku Ko~vo KK.
Additional classes of SRPs include those described in U.S. 4,201.824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRP's to convert terminal hydroxyl groups to trimellitate esters.
With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRPs may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S.
Preferably the geometric mean particle diameter of the detergent active particulates is no greater than 20% of the geometric mean particle diameter of the detergent base particles more preferably no greater than 10% and may even be below 5% of the geometric mean particle diameter of the detergent base particles. Generally in the detergent particles, no more than 25wrt% is derived from the detergent active particulates, preferably no greater than 10 wt°io. The invention may even be useful where the proportion of the detergent particles derived from the detergent active particulates is no greater than 5 or even no greater than 2 wt%.
As used herein the term "bulk densin-" refers to the uncompressed, untapped powder bulk density, as measured by pouring an excess of particulate sample through a funnel into a smooth metal vessel (e.g. a 500m1 volume cylinder) scraping off the excess off the heap above the rim of the vessel, measuring the remaining mass of powder and dividing the mass by the volume of the vessel.
The bulk density of the detergent particles produced and also of the detergent base particles is generally above 200 g/1 and may be as high as 1500 g/1. It is particularly preferred that the bulk density a finished detergent composition comprising the detergent particles produced according to the present invention is greater than 550 g/1, preferably greater than 600 g/1 or even above 650 g/1. The bulk density of the detergent particles produced is therefore generally from 400g/1 to 1100 g/1, generally above 500g/1 or even above 550 or 650g/1, generally less than 1 OOOg/1 or below 900g/1. The invention may be particularly useful for forming detergent particles having a low bulk density such as below 550 or even below 500 or 450 g/1.
The detergent base particles for use in the method of the present invention may comprise a single detergent ingredient in particulate form or may be a pre-mix of detergent ingredients.
Where the detergent base particles comprise a pre-mix, the separate detergent ingredients may simply be mixed together or may comprise a pre-formed particulate comprising any combination of two or more detergent ingredients, or mixtures thereof, optionally with single detergent ingredients. Suitable pre-formed particulates for the base particles may have been formed by spray-drying, agglomeration, marumerisation, extrusion or compaction, all of which methods for combining detergent ingredients are well-known in the art. Particularly preferred pre-formed particulates are powders obtained from spray-drying processes, agglomerates and extrudates.
Spray-dried powders are particularly useful. Pre-formed particulates made according to at least one low shear mixing step. for example in a fluidised bed. for example by fluid bed agglomeration are particularly preferred. Particularly preferred panicles are as described in our co-pending application filed today under reference number CW2158F.
Suitable spray-drying processes for forming such pre-formed particulates are described for example in EP-A-763594 or EP-A-437888. Suitable processes for forming pre-formed particulates which are agglomerates are described for example in W093/25378, EP-A-367339, EP-..A-420317 or EP-A-506184 and suitable processes for forming pre-formed particulates by extrusion are described for example in W091/02047.
Such pre-formed particulates may be added to the mixer in their wet or dry state. They are preferably added to the mixer in their dry state as addition in their wet state may have an adverse effect on flow into the mixer. Alternatively it may be preferred that the pre-formed particulates are formed in a first stage of a moderate to low shear mixer and the detergent active particulates are added in a second stage so that the pre-formed particulates may be in a wet state when they are contacted with the detergent active particulates. Thus, the pre-formed particulate may be for example an agglomerate, blown powder or extrudate which has not yet undergone a final drying stage.
Generally this means that a solvent used as a binding agent for the processing is present in higher amounts than are desirably present in a finished particulate detergent. Generally the solvent is water and wet particulates will have a free water content for example of froml5 to 30 wt % of the pre-formed particulate. Often, however, the pre-formed particulate will already have undergone a drying step prior to addition to the mixer so that the water content will be below 15 wt %, preferably below 10 wt %. Generally the free water content of the detergent base particles on entry into the mixer will be below 1 S wt %, preferably below 10 wt %.
It may be preferred that the detergent base particles comprise a surfactant or mixture of surfactants. Suitable surfactants are described below. The surfactant content of the detergent base particles or a pre-formed particulate component forming all or part of the detergent base particles is preferably from 5 to 80 % by weight of the particulate component.
Amounts of surfactants above 10 or even above 30% may be preferred. Amounts of surfactant below 70% or even below 50% may be preferred. Where the detergent base pre-formed particulate component comprises surfactant, generally it will in addition comprise a builder or alkalinity agent such as sodium carbonate, zeolite, or phosphate. For example, each of these components individually, or in mixtures may be present in amounts above 5%, preferably above 10°~0 or even above 20% by weight of the content of the pre-formed particulate component. Particularly preferred builder components are sodium carbonate and/or zeolite. Zeolite A and zeolite MAP are both suitable.
The detergent base particles preferably also comprises an organic builder such as a poly carboxylic acid andior salt such as citric acid. tartaric acid. malic acid, succinic acid and their salts or a polymeric polycarboxylate such as polymers based on acrylic acids or malefic acids or co-polymers thereof. Such components are generally present in the particle at levels below 15 wt of the particulate component, preferably below 10 W % of the particulate component.
Other preferred ingredients in the pre-formed particulate component are chelants such as phosphonate chelants NTA, DTPA and succinic acid derivative chelants, as described below.
These components are preferably present in the detergent base particles in amounts below ~ wt or even below 2 wt ° o. Suds supressors andior soil release polymers and/or bleach activators are also preferred ingredients in pre-formed particulates.
Where the particulate components are detergent raw materials, any particulate detergent ingredient is suitable. These may be solid surfactants or soaps. or water soluble or dispersable polymeric materials, enzymes. bleaching components such as bleach activators or bleach salts such as peroxy salts. Highly suitable single ingredients in particulate form include inorganic components, particularly water-soluble inorganic components such as builders and bleach salts such as alkali metal percarbonates and/or perborates. These ingredients are discussed in more detail below .
Suitable detergent ingredients for incorporation either into the detergent particles themselves, or for post-addition to formulate a fully formulated detergent composition are discussed below.
The detergent active particulates are selected from perfumes, enzymes, photobleaches, catalysts, soil release polymers, suds suppressors, bleaching compounds, whitening agents and layered silicates.
Perfumes Preferred detergent active particulates comprise perfume. Any perfume or perfume composition can be used. However, it must be solid or in combination with other components so that it has a solid form. For example it may be loaded onto a particulate carrier such as zeolite, or any other known solid carrier, for example as described in W094/16046, ES93000006, EP-A-535942, and EP-A-294206. More preferably it is present in encapsulated form.
Suitable encapsulates are described for example in W094/12613, EP-A-539025, EP-A-478326, EP-A-383406, EP-A-382464, EP-A-346034, EP-A-70719. Particularly preferred encapsulates comprise starch.
Preferred perfumes contain at least one component with a low molecular weight volatile component, e.g. having a molecular weight of from 150 to 450 or preferably 350. Preferably, the perfume component comprises an oxygen-containing functional group. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.
Enzymes The detergent active particulates may comprise one or more enzymes. Suitable enzymes include the commercially available lipases, cutinases, amylases. neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazvm, and Esperase by Novo Industries A/S
(Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Preferred amylase enzymes may be those described in PCT/ US 9703635, and in W095/26397 and W096/23873. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001%
to 0.5% by weight based on the content in the final detergent composition. The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcalieenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcalieenes, which is described in EP-B-0218272. Another preferred lipase is obtained by cloning the gene from Humicola lanuy'nosa and expressing the gene in Aspereillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414. Huge-Jensen et al, issued March 7, 1989.
Photobleaches Preferred detergent active particulates comprise photobleach particles.
Preferred photo-bleaches herein comprise a compounds having a porphin or porphvrin structure.
Porphin and porphvrin, in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub-class of porphin. The references to porphin in this application will include porphyrin. The porphin structures preferably comprise a metal element or canon, preferably Ca, Mg, P. Ti, Cr, Zr, In. Sn or Hf, more preferably Ge, Si or Ga, or more preferably A1 , most preferably Zn. It can be preferred that the photo-bleach or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pvridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.
The photo-bleaching compound or component can have solubilizing groups as substituents.
Alternatively, or in addition hereto the photo-bleaching agent can comprise a polymeric component capable of solubilizing the photo-bleaching compound, for example PVP, PVNP, PVI
or co-polymers thereof or mixtures thereof.
Highly preferred photo-bleaching compounds have a phthalocyanine structure, which preferably have the metal elements or canons described above. The phthalocyanines can be substituted, suitable examples include the phthalocyanine structures which are substituted at one or more of the l -4, 6. 8-11, 13, 15-18, 20, 22-25, 27 atom positions.
One preferred group of photobleaches comprise a polymeric component and a photobleaching component integrated with one another, whereby the weight ratio of polymeric component to photobleaching component is from 1:1 to 1000:1, preferably 20:1 to 100:1.
Particularly preferred polymeric compounds are formed from monomeric units selected from N-vinylpyrolidone, N-vinylacetamide, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyltriazole, 4-vinylpyridine arid 4-vinylpyrilidine-N-oxide. Preferred photo-bleaching compounds are metals, preferably zinc, phthalocyamines or aluminium. Such photo-bleaches are described in GB
2329397A.
Soil Release Polymers Preferred soil release polymers (SRPs) typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segments.
This can enable stains occurring subsequent to treatment with the SRP to be more easily cleaned in later washing procedures. Preferred SRPs include oligomeric terephthalate esters, typically prepared by _g_ processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one. nvo, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
Suitable SRPs include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P.
Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRPs include the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters ofU.S. 4,711,730. December 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly-(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857. October 27, 1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRPs useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.
SRPs also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the Cl-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20°C as a 2% aqueous solution. Such materials are available as METOLOSE SM 100T"' and METOLOSE SM200T"', which are methyl cellulose ethers manufactured by Shin-etsu Kagaku Ko~vo KK.
Additional classes of SRPs include those described in U.S. 4,201.824, Violland et al. and U.S. 4,240,918 Lagasse et al.; and SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRP's to convert terminal hydroxyl groups to trimellitate esters.
With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRPs may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S.
4,525,524 Tung et al., and U.S. 4,201,824, Violland et al.
Suitable soil release polymers may be selected from: (a) alkyl and hydroxyalkyl ethers of cellulose containing from one to four carbon atoms in the alkyl moiety and having a molar degree of substitution of from 1.5 to 2.7 and a number average molecular weight of from 2000 to 100000; (b) polymers comprising ethylene terephthalate and polyethylene oxide terephthalate at a mole ratio of from 1:10; (c) polymers comprising propylene terephthalate and polyethylene oxide terephthalate at a mole ratio of from 1:10 to 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight of from 500 to 10000 and said soil release agent having a number average molecular weight of from 1000 to 100000; and (d) polymers comprising ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide inany ratio such that the mole ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is from 1:10 to 10:1, said polyethylene oxide units and said polypropylene oxide units each having a number average molecular weight of from 250 ti 10000 and said soil release agent having a number average molecular weight of from 1000 to 100000; and mixtures thereof; as described in more detail in EP-A-271312.
Suds Supressors The detergent active particulates may comprise suds supressors. Suitable suds suppressing systems may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds or soap.
By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also t~rpically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable anti foam compounds include the monocarboxvlic fatty acids and soluble salts thereof as described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1 g-C40 ketones (e.g. stearone) N-allylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlorniazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters. A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%. such as DC0544, commercially available from Dow Corning; and (c) an inert carrier fluid compound, most preferably comprising a C16-CI g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80°ro, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof. with a melting point of from 45°C to 80°C.
Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone. such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers.
such as copolymers of laic and acrylic acid.
Bleaching Compounds The detergent active particulates may comprise one or more bleaching compounds.
Suitable bleaching compounds include bleach activators, pre-formed peracids and peracid salts such as alkali metal percarbonate and/or perborate. The chemical nature of these components is discussed in more detail below in the section entitled "Detergent Ingredients". Preferred bleach compounds are bleach activators such as TAED, NOBS, ISONOBS etc, as discussed below, and the persalts such as alkali metal percarbonate and/or perborate. Sodium salts are particularly preferred.
Whitenin~Agents Suitable whitening agents include hydrophilic optical brighteners such as include those having the structural formula:
R~ R, ON H ~I N O
N OON O ~_~ O N 00 ~T
ON H H N \
R2 S~3M S~3M R~
wherein RI is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a canon such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular br-ightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation.
Tinopal-CBS-a and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxvethyl-N-2-methylamino and M is a canon such as sodium, the brightener is 4.4'-bis[(4-anilino-6-(N-2-hvdroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
This particular brightener species is marketed as Tinopal 5BM-GXT"' by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4.4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species are sold by Ciba Geigy Corporation as Tinopal-DMS-XTM and Tinopal AMS-GXTM
Layered Silicates Suitable crystalline layered silicates are described for example in US
4,664,839.
Crystalline layered silicates rich in delta-phase are preferred. such as those described in W097/I 9156.
Cata~s The detergent active particulates may also comprise catalyst particulates.
Suitable catalysts include transition metal-containing bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activiy, such as copper, iron or manganese cations, an auxiliary metal canon having little or no bleach catalytic activity, such as zinc or aluminium cations, and a sequestrant/chelant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediamine tetraacetic acid, ethylenediamine tetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in US 4,430,243.
Other types of bleach catalysts include the manganese-based complexes disclosed in US
Suitable soil release polymers may be selected from: (a) alkyl and hydroxyalkyl ethers of cellulose containing from one to four carbon atoms in the alkyl moiety and having a molar degree of substitution of from 1.5 to 2.7 and a number average molecular weight of from 2000 to 100000; (b) polymers comprising ethylene terephthalate and polyethylene oxide terephthalate at a mole ratio of from 1:10; (c) polymers comprising propylene terephthalate and polyethylene oxide terephthalate at a mole ratio of from 1:10 to 10:1, said polyethylene oxide terephthalate containing polyethylene oxide units with a number average molecular weight of from 500 to 10000 and said soil release agent having a number average molecular weight of from 1000 to 100000; and (d) polymers comprising ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide inany ratio such that the mole ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is from 1:10 to 10:1, said polyethylene oxide units and said polypropylene oxide units each having a number average molecular weight of from 250 ti 10000 and said soil release agent having a number average molecular weight of from 1000 to 100000; and mixtures thereof; as described in more detail in EP-A-271312.
Suds Supressors The detergent active particulates may comprise suds supressors. Suitable suds suppressing systems may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds or soap.
By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also t~rpically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable anti foam compounds include the monocarboxvlic fatty acids and soluble salts thereof as described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1 g-C40 ketones (e.g. stearone) N-allylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlorniazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters. A preferred suds suppressing system comprises:
(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%. such as DC0544, commercially available from Dow Corning; and (c) an inert carrier fluid compound, most preferably comprising a C16-CI g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80°ro, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof. with a melting point of from 45°C to 80°C.
Other highly preferred suds suppressing systems comprise polydimethylsiloxane or mixtures of silicone. such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers.
such as copolymers of laic and acrylic acid.
Bleaching Compounds The detergent active particulates may comprise one or more bleaching compounds.
Suitable bleaching compounds include bleach activators, pre-formed peracids and peracid salts such as alkali metal percarbonate and/or perborate. The chemical nature of these components is discussed in more detail below in the section entitled "Detergent Ingredients". Preferred bleach compounds are bleach activators such as TAED, NOBS, ISONOBS etc, as discussed below, and the persalts such as alkali metal percarbonate and/or perborate. Sodium salts are particularly preferred.
Whitenin~Agents Suitable whitening agents include hydrophilic optical brighteners such as include those having the structural formula:
R~ R, ON H ~I N O
N OON O ~_~ O N 00 ~T
ON H H N \
R2 S~3M S~3M R~
wherein RI is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a canon such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular br-ightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation.
Tinopal-CBS-a and Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxvethyl-N-2-methylamino and M is a canon such as sodium, the brightener is 4.4'-bis[(4-anilino-6-(N-2-hvdroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
This particular brightener species is marketed as Tinopal 5BM-GXT"' by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4.4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species are sold by Ciba Geigy Corporation as Tinopal-DMS-XTM and Tinopal AMS-GXTM
Layered Silicates Suitable crystalline layered silicates are described for example in US
4,664,839.
Crystalline layered silicates rich in delta-phase are preferred. such as those described in W097/I 9156.
Cata~s The detergent active particulates may also comprise catalyst particulates.
Suitable catalysts include transition metal-containing bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activiy, such as copper, iron or manganese cations, an auxiliary metal canon having little or no bleach catalytic activity, such as zinc or aluminium cations, and a sequestrant/chelant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediamine tetraacetic acid, ethylenediamine tetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in US 4,430,243.
Other types of bleach catalysts include the manganese-based complexes disclosed in US
5,246,621 and US 5,244,594. Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-O)1(u-Oac)2(1,4,7-trimethul-1,4,7-triazacyclononane)2-(C1O4)2, MnIV4(u-O)6(1,4,7-triaxacyclononane)4-(C1O4)2, MnIIIMnIV4(u-O)1(u-Oac)2-(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C1O4)3, and mixtures thereof. Others are described in EP-A-549272. Other suitable ligands include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclonanone, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
For examples of suitable bleach catalysts see US 4,246,612 and US 5.227,084.
See also US 5,194,416 which teaches nononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclonanone)(OCH3)3-(PF6). Still another type ofbleach catalyst as disclosed in US
5,114,606 is a water-soluble complex of manganese (III) and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH
groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2Mn)ZI(u-O)2MnNbipy2]-(C1O4)3.
Further suitable bleach catalysts are described for example in EP 408131 (cobalt complex catalysts) EP 384503 and 306089 (metallo-porphyrin catalysts) US4,728,455 (manganese/multidentate ligand catalyst) US 4,711,748 and EP 224952 (absorbed manganese on aluminosilicate catalyst) US 4.601,845 (aluminosilicate support with manganese and zinc or magnesium salt) US 4,626,373 (manganese/ligand catalyst), US 4,119,557 (ferric complex catalyst), German Patent specification 2054019 (cobalt chelant catalyst), Canadian 866191 (transition metal-containing salts), US 4.430.243 (chelants with manganese cations and non-catalytic metal cations), and US 4,728.455 (manganese gluconate catalysts).
The preferred detergent active particulates comprise perfume, photobleach and/or catalyst. Perfume and/or photobleaches are particularly preferred. In a particularly preferred aspect of the invention, the detergent active particulates comprise encapsulated perfume. In a further particularly preferred aspect of the invention, the detergent active particulates comprise photobleach.
The preferred proportion of detergent active particulates to detergent base powder will vary dependent upon the relative particle sizes of these two components.
Preferably in the final detergent composition the weight percentage of any one of the detergent active particulates will be no greater than l Owt%, preferably below 5 wt°io or even below 2 or 1 w~t% of the detergent base particles. In particular where the proportion of detergent active particulates is as low as 5 or 2 or 1 W°ro of the detergent base powder, preferably the geometric mean particle size of the detergent active particulates is no greater than 20%, preferably no greater than 10 % or even below 5 or even 2 or 1 % of the geometric mean panicle size of the detergent base particles.
The detergent particles themselves may contain all of the ingredients of a full formulated detergent or may be mixed with additional detergent components such as individual detergent ingredients in particulate form or pre-formed detergent panicles as described above which may form part of the detergent base particles. The individual detergent ingredients in particulate form may be any of the detergent ingredients described below, in a particulate form. Preferably, detergent compositions of the present invention comprise more than 30 wt%, more preferably more than 50 wt°io or even as high as 80 or 90 wt% or even 95 wt% of the detergent particles according to the present invention. The higher the level of detergent particles of the present invention, the greater the benefits of the invention in terms of promoting uniform dosages of detergent from a package of particulate detergent or in a unit dosage which is formed into a tablet.
The processes of the invention may comprise the step of adding to the mixer a binder to facilitate production of the desired detergent particles. Generally such a binder will be liquid in the form of a solution or melt and will be added by spraying either directly into the mixer or onto the particulate components as they travel into the mixer. Preferably the binder is added directly into the mixer for example by spraying. The binder is added for purposes of enhancing agglomeration by providing a binding or sticking agent for detergent components. The binder may be any conventional detergent binding agent, preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrvlates, organic acids or their salts such as citric acid or citric salts. and mixtures thereof.
Other suitable binder materials includine those listed herein are described in Beerse et al, US
Patent number 5108646 (Procter and Gamble Company), the disclosure of which is incorporated herein by reference. The binder must be compatible with the detergent active particulate as will be appreciated by persons skilled in the an. Thus, where the stability of the detergent active particulate is adversely affected by water, the binder will be substantially water-free.
Thus, in one aspect of the invention, a first feed stream of detergent base powder is fed into the mixer and in addition a second feed stream comprising a detergent active particulates is fed into the mixer and binder is also present in the mixer. The binder may be fed directly via a third stream into the mixer or it may be contacted with the detergent base particles or detergent active particulates prior to one or both of these feed streams entering the mixer, for example the detergent active particulate (or a proportion of the base particles] may be entrained in the binder.
Where the mixer is divided into different zones, the three components may be fed into the same zone or optionally may be fed into different zones. In a preferred embodiment of the invention, the detergent base particles and detergent active particulates will be pre-mixed prior to addition of the binder.
In a further preferred aspect of the invention, after mixing of the detergent base particles and detergent active particulates, so that adhesion of the two components has taken place, a further liquid component is applied to the outside of the particles produced.
This further coating may be the same chemical composition as the binder or may be any of the other coating materials or detergent ingredients described below.
The moderate to low shear mixer to be used in the present invention may be for example a Lodige KM (trademark) (Ploughshare) moderate speed mixer, or mixer made by Fukae, Draes, Schugi or similar brand mixers which mix with only moderate to low shear. The Lodige KM
(ploughshare) moderate speed mixer which is a preferred mixer for use in the present invention comprises a horizontal hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached. Preferably, the shaft rotates at a speed of from about 1 S rpm to about 140 rpm, more preferably from about 80 rpm to about 120 rpm. The grinding or pulverizing is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm. Other mixers similar in nature which are suitable for use in the process include the Lodige PloughshareT"" mixer and the Drais~ K-T 160 mixer. Generally, in the processes of the present invention, the shear will be no greater than the shear produced by a Lodige KM mixer with the tip speed of the ploughs below 10 m/s, or even below 8mls or even lower.
Preferably, the mean residence time of the various starting detergent ingredients in the low or moderate speed mixer is preferably in range from about 0.1 minutes to about 30 minutes, most preferably the residence time is about 0.5 to about ~ minutes. In this way, the density of the resulting detergent agglomerates is at the desired level.
Other suitable mixers for use in the present invention are low or very low shear mixers such as rotating bowl agglomerators, drum agglomerators, pan agglomerators and fluid bed agglomerators.
Fluid bed agglomerators are particularly preferred. Typical fluidised bed agglomerators are operated at a superficial air velocity of from 0.1 to 4 m/s, either under positive or negative pressure. Inlet air temperatures generally range from -10 or 5°C up to 250°C. I-Iowever inlet air temperatures are generally below 200°C, or even below 150°C. The fluidized bed granulator is preferably operated such that the flux number FN of the fluid bed is at least about 2.~ to about 4.5. Flux number (FIvTm) is a ratio of the excess velocity (Ue) of the fluidisation gas and the particle density (pp) relative to the mass flux (q,;q) of the liquid sprayed into the bed at a normalized distance (D°) of the spraying device. The flux number provides an estimation of the operating parameters of a fluidized bed to control granulation within the bed.
The flux number may be expressed either as the mass flux as determined by the following formula:
FNm = log~oL {PaUe)/9nq~
or as the volume flux as determined by the formula:
FN,. = logio~{Ua/q~aq~
where q,,,;g is the volume of spray into the fluid bed. Calculation of the flux number and a description of its usefulness is fully described in WO 98/58046 the disclosure of which is herein incorporated by reference.
In addition, the fluidized bed is generally operated at a Stokes number of less than about 1, more preferably from about 0.1 to about 0.5. The Stokes number is a measure of particle coalescence for describing the degree of mixing occurring to particles in a piece of equipment such as the fluid bed. The Stokes number is measured by the formula:
Stokes number = 4pvd/9u wherein p is the apparent particle density, v is the excess velocity, d is the mean particle diameter and a is the viscosity of the binder. The Stokes number and a description of its usefulness is described in detail in ~'l'O 99/03964, the disclosure of which is herein incorporated by reference.
Thus, where the mixer is a fluid bed mixer, detergent base particles of the present invention are passed into a fluid bed optionally having multiple internal "stages" or "zones". A
stage or zone is any discrete area within the fluid bed, and these terms are used interchangeably herein. The process conditions within a stage may be different or similar to the other stages in the fluid bedldryer. It is understood that two adjacent fluid beds are equivalent to a single fluid bed having multiple stages. The various feed streams of detergent base particles and detergent active particulates can be added either at the same or at the different stages, depending on, for example, the particle size and moisture level of the feed stream. Feeding different streams to different stages can minimize the heat load on the fluid bed. and optimize the particle size and increase uniformity of the shape of the detergent particles produced.
The bed is typically fluidized with heated air in order to dry or partially dry moisture such as the binder liquids from the ingredients in the fluid bed. Where binder is sprayed into the fluid bed the spraying is generally achieved via nozzles capable of delivering a fine or atomized spray of the binder to achieve intimate nixing with the particulates.
Typically, the droplet size from the atomizer is less than about 2 times the particle size. This atomization can be achieved either through a conventional two-fluid nozzle with atomizing air, or alternatively by means of a conventional pressure nozzle. To achieve this type of atomization, the solution or slurry rheology is may have a viscosity of less than about 500 centipoise, preferably less than about 200 centipoise at the point of atomization. While the nozzle location in the fluid bed may be in most any location, the preferred location is a positioning that allows a vertical down spray of any liquid components such as binder. This may be achieved for example, using a top spray configuration. To achieve best results, the nozzle location is placed at or above the f7uidized height of the particles in the fluid bed. The fluidized height is typically determined by a weir or overflow gate height. The agglomeration/granulation zone of the fluid bed may be followed by an optional coating zone, followed by a drying zone and a cooling zone. Of course, one of ordinary skill in the art will recognize that alternative arrangements are also possible to achieve the resultant particles of the present invention.
Typical conditions within a fluid bed apparatus of the present invention include: (i) a mean residence time from about 1 to about 20 minutes, (ii) a depth of unfluidised bed of from about 100 to about 600 mm, (iii) a droplet spray size of less than 2 times the mean particle size in the bed, which is preferably not more than about 100 micron more preferably not more than 50 microns, (iv) spray height generally from 150 to 1600 mm of spray height from the fluid bed plate or preferably 0 to 600mm from the top of the fluid bed , (v) from about O.l to about 4.0 m/s.
preferably 1.0 to 3.Orrvs of f7uidizing velocity and (vi) from about 12 to about 200 °C of bed temperature, preferably 15 to 100°C. Once again. one of ordinary skill in the art will recognise that the conditions in the fluid bed may vary depending on a number of factors.
The detergent particles produced in the mixer can be further processed by adding a coating agent to improve the particle colour, increase the particle whiteness or improve the particle flowability after the detergent particles exit the mixer or the dryer if an optional drying step is added subsequently to the mixer or in a later stage in the mixer, to obtain the high density granular detergent compositions produced by the processes of the invention.
Those skilled in the art will appreciate that a wide variety of methods may be used to dry as well as cool the exiting detergent without departing from the scope of the invention. Since the mixer can be operated at relatively low temperatures, the need for cooling apparatus is generally not required in the present process which thereby further reduces manufacturing costs of the final product.
Another optional processing step includes continuously adding a coating agent such as zeolite and/or fumed silica to the mixer to facilitate free f7owabiliy of the resulting detergent particles and to prevent over agglomeration. Such coating agents generally have a mean particle size below 100 microns, preferably below 60 microns, even more preferably below 50 microns.
Any coating stage may take place either immediately after formation of the detergent particles of the invention either before or after any drying step and optionally after the detergent particles have been mixed with additional detergent ingredients for forming a fully formulated detegent composition. Preferably any such coating agent will also have detergent active properties. A particularly preferred coating agent is a surfactant or aqueous solution of surfactant.
Detergent ingredients which are suitable as ingredients of the base powder, and/or as ingredients of the detergent active particulates and/or as ingredients of any additional ingredients added to the detergent particles of the present invention to form the fully formulated detergent compositions of the invention are described below.
Deter eg nt Ingredients Surfactant Suitable surfactants for use in the invention are anionic, nonionic, ampholytic, and zwitterionic classes of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4.259,217 issued to Murphy on March 31, 1981.
Preferably. the detergent particle of the present invention and compositions comprising such particles comprises an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition.
These can include salts (including, for example, sodium, potassium, ammonium. and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.
The anionic surfactants may be present in the detergent particle in amounts below 25 w or even below 20 wrt % but in a final detergent composition comprising the particle, is preferably present at a level of from 0.1 % to 60%. more preferably from 1 to 40%, most preferably from 5% to 30% by weight.
Other anionic surfactants include the anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxvlates and soaps ("allyl carboxyls") such as water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-I-octanoic acid and 2-pentyl-I-heptanoic acid. Certain soaps may also be included as suds suppressors. Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R1) CH2 COOM, wherein R is a CS-C I ~ linear or branched alkyl or alkenyl group, R 1 is a C I -C4 alkyl group and M is an alkali metal ion. Other anionic surfactants include isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the CS-CIA acyl-N-(CI-C4 alkyl) and -N-(CI-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein). Alkyl sulfate surfactants are preferably selected from the linear and branched primary CI0-CI g alkyl sulfates, more preferably the CI I-CIS branched chain alkyl sulfates and the CIA-C14 linear chain alkyl sulfates. Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C 18 allyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the allyl ethoxvsulfate surfactant is a C11-Clg, most preferably C11-CI5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5.
moles of ethylene oxide per molecule.
Preferred surfactant combinations are mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants optionally with cationic surfactant. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids. alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Essentially any alkoxvlated nonionic surfactant or mixture is suitable herein.
The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are particularly suitable for use herein.
Particularly preferred are the condensation products of straight or branched, primary or secondary alcohols having an alkyl group containing from 6 to 22 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONRIZ wherein : RI is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl: and R2 is a C5-C31 hydrocarbyl;
and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Suitable alkylpolysaccharides for use herein are disclosed in LT.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units. Preferred alkylpolyglycosides have the formula:
R2O(CnH2n0)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3(OR4)xN0(RS)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are CIO-Clg alkyl dimethylamine oxide, and CIO-18 acylamido alkyl dimethylamine oxide.
Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
Betaines such as C12-18 dimethyl-ammonio hexanoate and the CIO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines and sultaine surfactants are exemplary 2witterionic surfactants for use herein.
Suitable cationic surfactants to be used herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono C6-C16, preferably C6-Cl0 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Cationic ester surfactants such as choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529 are also suitable as are cationic mono-alkoxylated amine surfactants preferably of the general formula I:
R' /((CH2)2-a0)~-tH
N+ /
CH3/ \CH3 wherein R 1 is C 10-C 1 g hydrocarbyl and mixtures thereof, especially C 10-C
14 alkyl, preferably C10 and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide. The levels of the cationic mono-alkoxylated amine surfactants in the detergent compositions of the invention are generally from 0.1 % to 20%, preferably from 0.2% to 7°io, most preferably from 0.3% to 3.0% by weight.
Cationic bis-alkoxvlated amine surfactant such as +/CH~CH20H
X
CH / \CH2CH20H
are also useful, wherein R1 is C10-Clg hydrocarbyl and mixtures thereof, preferably C10, C12 C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride.
Bleach Activator The detergent particles or detergent compositions containing them preferably comprise a bleach activator, preferably comprising an organic peroxyacid bleach precursor. It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxy acid bleach precursor, as defined herein. The production of the organic peroxyacid occurs then by an in situ reaction of the precursor with a source of hydrogen peroxide. The bleach activator may alternatively, or in addition comprise a preformed peroxy acid bleach.
It is preferred that the bleach activator is present in the detergent particle. It may be preferred that the bleach activator is present as a separate, admixed particle. Preferred hydrophobic peroxy acid bleach precursor preferably comprise a compound having an oxy-benzene sulphonate group, preferably NOBS, DOBS, LOBS and/ or NACA-OBS.
Preferred hydrophilic peroxy acid bleach precursors preferably comprises TAED.
Peroxyacid Bleach Precursor Peroxvacid bleach precursors are compounds which react with hydrogen peroxide in a perhvdrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as O
X-C-L
where L is a leaving group and X is essentially any functionality. such that on perhydroloysis the structure of the peroxyacid produced is O
X-C-OOH
For the purpose of the invention, hydrophobic peroxyacid bleach precursors produce a peroxy acid of the formula above wherein X is a group comprising at least 6 carbon atoms and a hydrophilic peroxyacid bleach precursor produces a peroxvacid bleach of the formula above wherein X is a group comprising 1 to 5 carbon atoms.
The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition. Preferred L groups are selected from the group consisting of:
Y R3 RsY
-O ~ , -O U Y , and -O
-N-C-R -N N -N-C-CH-R
I ' , I I
R3 ~ R3 Y
I
Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2 , O Y O
-NCH2-C\NR4 _N~ ~NR4 -~C-R ~C/ , ' II
O
-O-C=CHR4 , and -N-S-CH-R4 and mixtures thereof, wherein RI is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -S03 M+, -C02 M+, -S04 M+, -N+(R3)4X and O<--N(R3)3 and most preferably -S03 M+ and -C02 M+ wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a canon which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
Preferably, M is an alkali metal, ammonium or substituted ammonium canon, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Peroxyacid bleach precursor compounds are preferably present in final detergent compositions at a level of from 0.5% to 30% by weight, more preferably from 1 % to 15% by weight, most preferably from 1.5% to 10% by weight. The ratio of hydrophilic to hydrophobic bleach precursors, when present, is preferably from 10:1 to 1:10, more preferably from 5;1 to 1:5 or even from 3:1 to 1:3. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
Allyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide t'~pe include the N-,IvT,IvTINI
tetra acet<~lated alkylene diamines wherein the all.~~lene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains I, 2 and 6 carbon atoms.
Tetraacetyl ethylene diamine (TAED) is particularly preferred as hydrophilic peroxy acid bleach precursor.
Other preferred alkyl percarboxvlic acid precursors include sodium 3,5.5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (HOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
R~ -CNR2C-L R~ NCR2CL
O R5 O or R5 O O
wherein R1 is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R5 is H
or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. RI preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. RI may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, aryl, wherein said RZ may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
RS is preferably H
or methyl. R1 and R5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It can be preferred that RI and RS forms together with the nitrogen and carbon atom a ring structure.
Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6-nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A-0170386.
Perbenzoic acid precursor compounds which provide perbenzoic acid on perhydrolysis benzoxazin organic peroxyacid precursors, as disclosed for example in EP-A-332294 and EP-A-482807 and cationic peroxvacid precursor compounds which produce cationic peroxyacids on perhydrolysis are also suitable. Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127.82: 5.093,022;
5,106,528; U.K.
1,382.594: EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxvacid precursors are described in UK
Patent Application No. 9407944.9 and US Patent Application Nos. 08!298903, 08/298650, 08; 298904 and 08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
The particles or compositions of the present invention may contain, in addition to, or as an alternative to an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 0.1% to 15% by weight, more preferably from 1% to 10% by weight. A preferred class of organic peroxyacid compounds are the amide substituted compounds as described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxvtetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Peroxide Source Inorganic persalts are a preferred source of peroxide. Preferably these salts are present at a level of from 0.01% to 50% by weight, more preferably of from 0.5% to 30% by weight of the particle or composition of the invention. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB02H202 or the tetrahydrate NaB02H202.3H20.
Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03.3H202, and is available commercially as a crystalline solid. Potassium peroxymonopersulfate is another inorganic perhydrate salt suitable for use herein.
Chelants As used herein, chelants refers to detergent ingredients which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacit)~, but preferably selectively bind heave metal ions such as iron, manganese and copper.
Chelants are generally present in the detergent particle or final detergent composition at a level of from 0.005% to 10%, preferably from 0.1% to 5°0, more preferably from 0.25% to 7.5%
and most preferably from 0.3% to 2% by weight of the compositions or component Suitable chelants include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates, preferably, diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
Other suitable chelants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof, and iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516.102 are also suitable herein. The ~-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable. EP-A-476.257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen.
keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant.
Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N.N'-disuccinic acid (EDDS) and 1,l hvdroxyethane diphosphonic acid or the alkali metal, alkaline earth metal.
ammonium, or substituted ammonium salts thereof, or mixtures thereof. In particular the chelating agents comprising a amino or amine group can be bleach-sensitive and are suitable in the compositions of the invention.
Water-Soluble Builder Compound The component or compositions herein preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1 %
to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight.
The detergent compositions of the invention may comprise phosphate-containing builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8°~o to 40%. The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid, tarnonic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxvsuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1.398,422 and in U.S.
Patent No. 3,936.448, and the sulfonated pyrolysed citrates described in British Patent No.
1,439.000. Preferred polycarboxylates are hydroxy carboxylates containing up to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
Borate builders and builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolvphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate. sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Examples of organic polymeric compounds include the water soluble organic homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with malefic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Partially Soluble or Insoluble Builder Compound The panicles or detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight. Examples of largely water insoluble builders include the sodium aluminosilicates.
As mentioned above, it may be preferred in one embodiment of the invention, that only small amounts of alumino silicate builder are present.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(A102)z(Si02)y]. x120 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite .A, Zeolite B, Zeolite P. Zeolite X. Zeolite HS and mixtures thereof. Zeolite A has the formula:
Na 12 [A102) 12 (Si02)12~. xH20 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6 [(A102)g6(Si02)106~~
276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
The zeolite MAP can be present at a level of from 1 % to 80%, more preferably from 15%
to 40% by weight. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2. Of particular interest is zeolite MAP
having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a median particle size d50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres. The d50 value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer, described herein. Other methods of establishing d50 values are disclosed in EP 384070A.
Other Deter eg nt Ingredients A preferred ingredients of the compositions herein are dyes and dyed particles or speckles, which can be bleach-sensitive. The dye as used herein can be a dye stuff or an aqueous or nonaqueous solution of a dye stuff. It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the detergent particles or speckles, preferably such that levels of dye solution are obtained up to 2% by weight of the dyed particle.
or more preferably up to 0.5% by weight, as described above. The dye may also be mixed with a non-aqueous carrier material, such as non-aquous liquid materials including nonionic surfactants.
Optionally, the dye also comprising other ingredients such as organic binder materials, which may also be a non-aqueous liquid.
The dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs include E104 - food yellow 13 (quinoline yellow), E110 - food yellow 3 (sunset yellow FCF), E131 -food blue 5 (patent blue V), Ultra Marine blue (trade name), E133 - food blue 2 (brilliant blue FCF), E140 - natural green 3 (chlorophyll and chlorphyllins), E141 and Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs may be Monastral Blue BV
paste (trade name) and,% or Pigmasol Green (trade name).
Another preferred ingredient of the particles or compositions of the invention is a perfume or perfume composition. Any perfume composition can be used herein.
The perfumes may also be encapsulated. Preferred perfumes containing at least one component with a low molecular weight volatile component , e.g. having a molecular weight of from 150 to 450 or preferably 350. Preferably, the perfume component comprises an oxygen-containing functional group. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.
Another highly preferred ingredient useful in the particles or compositions herein is one or more additional enzymes. Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred enzymes are discussed above with respect to the detergent active particulates.
The same enzymes are preferred as components of the detergent base powder or as additional detergent ingredients added to the detergent particles of the invention to form a fully formulated detergent.
The detergent particles or compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, preferably as a detergent active particulate component as mentioned above. Examples are commercially marketed by Ciba Geigy Corporation as Tinopal-LTNPA-GXT"' and Tinopal-CBS-XTM.
Others include Tinopal 5BM-GXT"', Tinopal-DMS-XT"' and Tinopal AMS-GXTM by Ciba Geigy Corporation.
Photo-Bleachine Agent As described above, photo-bleaching agents are preferred ingredients of the compositions and are preferably present in the form of the detergent active particulates as discussed above.
However, they may optionally be present in the detergent base particles or as additional detergent ingredients for addition to the detergent particles of the invention for forming the fully formulated detergnet compositions of the invention.
Oreanic Polymeric lnQredients Organic polymeric compounds are preferred additional herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. Bv organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quaternised ethoxylated (poly) amine clay-soil removali anti-redeposition agent in accord with the invention.
Organic polymeric compound is typically incorporated in the finished detergent compositions of the invention at a level of from 0.01°~o to 30%, preferably from 0.1°~o to 15%, most preferably from 0.5% to 10% by v~~eight of the compositions or component.
Terpolymers containing monomer units selected from malefic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000. are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
H3 ~ H3 X-~OCH2CH2)n i +-CH2-CH2~-CH2)a N+-CH2CH~0-~X
b (CH2CH20 ~ X (CH2CH20 ~ X
wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0: for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35: for cationic diamines (b=1), n is at least about 12 with a typical range of from about 12 to about 42.
Other dispersantsi anti-redeposition acents for use herein are described in EP-and US 4,659,80? and US 4.664,848.
Suds Suppressin System The suds supressing system is preferably also present in the form of the detergent active particulates as described above. Such components may however be present in the detergent base particles or as additional detergent ingredients for addition to the detergent particles of the invention for formulating a finished detergent composition.
Polymeric dye transfer inhibiting agents may also be present in the detergent particles or compositions of the invention. When present they are generally in amounts from 0.01 % to 10 %, preferably from 0.05% to 0.5% based on the final detergent compositions and are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolvmers or combinations thereof, whereby these polymers can be cross-linked polymers.
Polymeric soil release agents, which are described above are also preferably present as detergent active particulates. However they may be present alternatively or in addition, in the detergent base particles or as additional detergent ingredients for addition to the detergent particles of the invention for formulating a finished detergent composition.
Other optional ingredients suitable for inclusion in the compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.
Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. Also, preferably combined with a carbonate salt, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4.285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference), can be present.
The detergent compositions can include as an additional component a chlorine-based bleach. However, since the detergent.compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable. Alternatively, a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.
The chlorine-based bleach is such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCI-.
Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides. Specific examples include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-~.5-dimethylhydantoin. N-chlorosulfamide, Chloramine T, Dichloramine T. chloramine B and Dichloramine B. A preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof. A preferred chlorine-based bleach can be Triclosan (trade name).
Most of the above-described hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions.
Laundry Washine Method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from l Og to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
Preferred washing machines may be the so-called low-fill machines.
In a preferred use aspect the composition is forntulated such that it is suitable for hard-surface cleaning or hand washing. In another preferred aspect the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.
Examples Abbreviations used in the Examples In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS : Sodium linear C11-13 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate branched AS . branched Sodium alkyl sulfate as described in W099/19454 CxyAS . Sodium C 1 x - C 1 y alkyl sulfate C46SAS . Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS : Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide CxyEz : C 1 x-C 1 y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS : R2.N+(CH3)2(C2H40H) with R2 = C12 - C14 QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = C8 - C 11 APA : C8 - C10 amido propyl dimethyl amine Soap : Sodium linear alkyl carboxylate derived from an 80.!20 mixture of tallow and coconut fatty acids STS : Sodium toluene sulphonate CFAA : C12-Cl4 (coco) alkyl N-methyl glucamide TFAA . C16-C18 alkyl N-methyl glucamide TPKFA : C 12-C 14 topped whole cut fatty acids STPP . Anhydrous sodium tripolyphosphate TSPP . Tetrasodium pyrophosphate Zeolite A : Hydrated sodium aluminosilicate of formula Nal2(AlO2Si02)12.27H20 having a primary panicle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 : Crystalline layered silicate of formula d-Na2Si205 Citric acid . Anhydrous citric acid Borate : Sodium borate Carbonate . Anvdrous sodium carbonate with a particle size between 200~m and 900pm Bicarbonate . Anhydrous sodium bicarbonate with a particle size distribution between 400pm and 1200pm Silicate : Amorphous sodium silicate (Si02:Na20 = 2.0:1 ) Sulfate : Anhydrous sodium sulfate Mg sulfate . Anhydrous magnesium sulfate Citrate . Tri-sodium citrate dehydrate of activity 86.4%
with a particle size distribution between 425pm and 850~m MA/AA : Copolymer of 1:4 maleic/acrylic acid, average m. W. about 70,000 MA/AA ( 1 ) . Copolymer of 4:6 maleic/acrylic acid, average m. W. about 10,000 AA . Sodium polyacrylate polymer of average molecular weight 4,500 CMC : Sodium carboxymethyl cellulose Cellulose ether l cellulose ether with a degree of polymerization :Methy of 650 available from Shin Etsu Chemicals Protease . Proteolytic enzyme, having 3.3/o by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Protease I : Proteoh~tic enzyme. having 4% by weight of active enzyme, as described in VSO 95/10591. sold by Genencor Int. lnc.
Alcalase : Proteolvtic enzyme, having 5.3% by weight of active enzyme. sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase : Amylolyic enzyme, having I .6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
Lipase : Lipolytic enzyme, having 2.0% by weight of active enzyme. sold by NOVO Industries A/S under the tradename Lipolase Lipase (1) : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra Endolase : Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaB02.3H2 O.H2O2-PB1 . Anhydrous sodium perborate bleach of nominal formula NaB02.H 2O2 Percarbonate . Sodium percarbonate of nominal formula 2Na2C03.3H2O2 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt NAC-OBS : (6-nonamidocaproyl) oxybenzene sulfonate TAED : Tetraacetylethylenediamine DTPA . Diethylene triamine pentaacetic acid DTPMP . Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename bequest 2060 EDDS . Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer sodium salt.
Photoactivated : Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer Photoactivated :Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate HEDP : 1,1-hydroxyethane diphosphonic acid PEGx . Polyethylene glycol, with a molecular weight of x (typically 4,000) PEO : Polyethylene oxide, with an average molecular weight of 50,000 TEPAE : Tetraethylenepentaamine ethoxylate PVI . Polwinvl imidosole, with an average molecular weight of 20.000 PVP : Polyvinylpvrolidone polymer, with an average molecular weight of 60,000 PVNO . Polyvinylpvridine N-oxide polymer. with an average molecular weight of 50,000 PVPVI : Copolymer of polvvinylpvrolidone and vinylimidazole, with an average molecular weight of 20,000 QEA : bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3) bis((C2H50)-(C2H4 O))n, wherein n = from 20 to 30 SRP 1 . Anionically end capped poly esters SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) short block polymer PEI . Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Silicone antifoam:Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1 Opacifier . Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft under the tradename Lytron Wax : Paraffin wax HMSO . hexamethylene diamine tetra(ethylene oxide)24 The following are examples of the present invention.
EXAMPLE I
This Example illustrates a process according to this invention which produces uniform free flowing, good dispensing and dissolving detergent particles with uniformity of colour and particle shape. Multiple detergent starting ingredients are dry mixed in an orbital vertical screw mixer of 200kg batch size, and several batches prepared. This bulk premix is added into a horizontal rotating drum type mixer with internal baffles - a laboratory scale example having batch size 40kg. A proportion of premix is sampled and added to the mixer. The smaller particles which pose a segregation risk are dry mixed into the mixer.
Binding agent, C45AE7, is sprayed into the mixer using an air atomised nozzle.
The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further 1 minute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % ~'~'eight of Total Feed Drv materials added to the~remix Detergent premix* 98.48%
Photobleach 0.02°ro Perfume encaps type 1 0.5%
Perfume encaps type 2 0.2%
Binding agent C45AE7 alcohol ethoxylate 0.7%
Anti-caking agent Zeolite A 0.1 * = comprising of sodium linear alkyl benzene sulphonate ( 13.4wrt%), zeolite A (40°~0), sodium sulphate (23.5%), sodium carbonate (8.4%), magnesium sulphate (0.7wt%), EDDS
(0.4wt%), MA/AA (2.Swt%), soap (l.Swt%), QAS l(2.Owt%), HEDP (0.3wt%), optical brightener (O.Swt%), water (5.3wt%), diamine hexamethylene tetra (ethylene oxide) 24 (l.5wt%).
EXAMPLE II
This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in example 1, of composition as listed below. A proportion of premix is sampled and added to the mixer.
Binding agent, C45AE7 mixed with PEG 4000, is sprayed into the mixer using an air atomised nozzle. The premix of increased cohesivity is left to mix for 1 minute. The smaller particles which pose a segregation risk are dry mixed into the mixer. The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further 1 minute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % Weight of Total Feed Dry materials added to the premix Detergent premix* 98.48%
Photobleach 0.02%
Perfume encaps type 1 0.5%
Perfume encaps type 2 0.2%
Bindine agent C45AE7 alcohol ethoxvlate 1.0%
PEG4000 0.5%
Anti-caking a Zeolite A 0.2%
EXAMPLE III
This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in example I, of composition as listed below. A proportion of premix is sampled and added to the mixer.
Binding agent, C45AE5, is sprayed into the mixer using an air atomised nozzle. The premix of increased cohesivity is left to mix for I minute. The smaller particles which pose a segregation risk are dry mixed into the mixer. The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further 15 seconds. The product is run into a storage box.
Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % Weight of Total Feed Dry materials added to the premix Detergent premix* 97.78%
Photobleach 0.02%
Perfume encaps type 1 0.4%
Perfume encaps type 2 0.1 Binding aft C45AE5 alcohol ethoxylate 1.5%
Anti-cakin~agent Zeolite A 0.2%
EXAMPLE IV
This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in example 1, of composition as listed below. A proportion of premix is sampled and added to the mixer.
Bonding agent, C45AE7, is sprayed into the mixer using an air atomised nozzle. The premix of increased cohesivity is left to mix for 1 minute. The smaller particles which pose a segregation risk are dry mixed into the mixer. A further spray-on of bonding agent is applied to fix the small particles firmly to the surface of the larger host particles. The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further I
minute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % Weight of Total Feed Drv materials added to the_premix Detergent premix* 98.2%
Photobleach 0.02%
Perfume encaps type 1 0.5%
Perfume encaps type 2 0.2%
Binding fluid C45AE7 alcohol ethoxylate 1.0%
Anti-caking agent Zeolite A 0.08°~0 EXAWPLE V
This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in example 1, of composition as listed below. A proportion of premix is sampled and added to the mixer.
The fine segregatable particles are dispersed into a carrier fluid such as C45AE7 in a tank, using low shear agitation, mixed for 10 minutes. The suspension of fine particles in fluid is pumped to a spray nozzle and atomised onto the premix particles in the mixer.
The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further 1 minute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % Weight of Total Feed Drv materials added to the premix Detergent premix* 96.48%
Photobleach 0.02%
Binding fluid C45AE7 alcohol ethoxylate 3.0%
Anti-caking agent Zeolite A 0.5%
Further example compositions In the following examples all levels are quoted as % by weight of the full finished detergent composition:
TABLE
The following compositions are in accordance with the invention.
A B C D E F ParticleSpan E Sphericity ize Colour(Mean) (median, ifferenc Vim) of raw material compare to finished compositi n 1. S ra 50qm 1.8 .4 1.9 -dried ranules LAS .0 .0 11.0 .0 .0 .0 AS 1.0 C45AS 1.0 1.0 C16-C17 .0 .0 .0 branched S
DTPA, .5 .6 0.5 .7 1.0 .5 HEDP
nd/or EDDS
MgS04 .5 .4 .5 .4 .5 .5 Sodium 10.0 .0 .0 .0 .0 10.0 arbonate Sodium .0 .0 .0 5.0 .0 .0 ulphate eolite 18.0 0.0 18.0 10.0 0.0 17.0 A
IMA/AA or 1.0 1.5 1.0 .6 1.0 0.6 (QAS 1 1.0 0.5 1.0 .8 1.0 Brightener 0.1 0.05 .05 0.06 0.05 0.05 IHMEO 0.5 .5 1.0 .5 1.0 1.0 I
ISoap 1.5 1.0 1.5 1.5 (Component is within the ~i remix (Spray dried50.0 50.0 8.0 0.0 0.0 50.0 I
~granules (1 ) (Nonionic 5.0 Sodium .0 .0 .0 .0 5.0 OO~m 1.5 .0 1.5 carbonate Sodium .0 1.0 350~m 1.6 .5 1.5 ulphate QAS 1 .0 1.0 500~m .7 .0 .1 gglomerate Nonionic 10.0 500~m 1.9 .3 1.8 gglomerate SKS-6 / 12.0 350pm 1.8 14.6 1.9 LAS
gglomerate Silicone .5 .5 .0 .5 .5 500~m .0 14.3 1.5 ntifoam gglomerate SRP 1 ,5 ~ .5 .3 500~m .0 10.4 .0 AED .5 .5 .0 550~m .5 11.4 .6 ggiomerate SKS-6 3.5 3.5 9.0 3.5 5.0 O~m 1.9 6.0 1.7 powder AED 1.5 .0 80~m 1.7 9.5 1.6 powder Premix binder pplied to he premix (2) PEG 4000 5.0 PEG 1500 .0 S, LAS, 5.0 .0 MBAS
ater as 10.0 15.0 binder (removed on vying) Other additives os t-added to make the final detergent formulation . S ra -on materials Pertume .4 .2 .4 .4 .5 .3 WO 00!78908 PC'T/US00/16916 ..
5. D
added materials Premix 0.0 5.0 55.0 65.0 0.0 0.0 (2) Enzymes .0 1.5 1.0 1.3 1.2 1.5 (protease, lipolase, mylase, cellulase) NACAOBS 3.0 .5 .0 3.5 3.5 .5 Sodium 13.0 10.0 10.0 12.0 12.0 10.0 percarbonat Photobfeach0.02 0.02 .02 0.02 0.02 0.02 Perfume .7 .5 .6 .8 .9 .4 ncapsulate Citric .0 .0 .0 .0 .5 .0 acid Sodium 1.0 1.0 1.0 .5 1.5 1.5 rbonate peckle eolite .1 .3 A
AED .p gglomerate Silicone .0 ntifoam ggiomerate . Coatin pplied to premix (2) Burkeite .0 5.0 8.0 5.0 (applied in 30wt%
queous olution) Brightener .1 .1 Fillers up to 100%
Finished product Median OOpm OOpm OO~m 800~m800pmOOp.m particle size Span 1.4 1.2 1.4 1.2 1.4 1.6 (geometric tandard eviation) Roundness 1.30 1.20 1.35 1.40 1.45 1.40 (mean) hiteness 98.0 6.5 98.5 92.0 97.0 101.5 ~IW=L-3b Having thus described the invention in detail, it will be obvious to those skilled in the an that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.
For examples of suitable bleach catalysts see US 4,246,612 and US 5.227,084.
See also US 5,194,416 which teaches nononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclonanone)(OCH3)3-(PF6). Still another type ofbleach catalyst as disclosed in US
5,114,606 is a water-soluble complex of manganese (III) and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH
groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnIII(u-O)2MnIVN4)+and [Bipy2Mn)ZI(u-O)2MnNbipy2]-(C1O4)3.
Further suitable bleach catalysts are described for example in EP 408131 (cobalt complex catalysts) EP 384503 and 306089 (metallo-porphyrin catalysts) US4,728,455 (manganese/multidentate ligand catalyst) US 4,711,748 and EP 224952 (absorbed manganese on aluminosilicate catalyst) US 4.601,845 (aluminosilicate support with manganese and zinc or magnesium salt) US 4,626,373 (manganese/ligand catalyst), US 4,119,557 (ferric complex catalyst), German Patent specification 2054019 (cobalt chelant catalyst), Canadian 866191 (transition metal-containing salts), US 4.430.243 (chelants with manganese cations and non-catalytic metal cations), and US 4,728.455 (manganese gluconate catalysts).
The preferred detergent active particulates comprise perfume, photobleach and/or catalyst. Perfume and/or photobleaches are particularly preferred. In a particularly preferred aspect of the invention, the detergent active particulates comprise encapsulated perfume. In a further particularly preferred aspect of the invention, the detergent active particulates comprise photobleach.
The preferred proportion of detergent active particulates to detergent base powder will vary dependent upon the relative particle sizes of these two components.
Preferably in the final detergent composition the weight percentage of any one of the detergent active particulates will be no greater than l Owt%, preferably below 5 wt°io or even below 2 or 1 w~t% of the detergent base particles. In particular where the proportion of detergent active particulates is as low as 5 or 2 or 1 W°ro of the detergent base powder, preferably the geometric mean particle size of the detergent active particulates is no greater than 20%, preferably no greater than 10 % or even below 5 or even 2 or 1 % of the geometric mean panicle size of the detergent base particles.
The detergent particles themselves may contain all of the ingredients of a full formulated detergent or may be mixed with additional detergent components such as individual detergent ingredients in particulate form or pre-formed detergent panicles as described above which may form part of the detergent base particles. The individual detergent ingredients in particulate form may be any of the detergent ingredients described below, in a particulate form. Preferably, detergent compositions of the present invention comprise more than 30 wt%, more preferably more than 50 wt°io or even as high as 80 or 90 wt% or even 95 wt% of the detergent particles according to the present invention. The higher the level of detergent particles of the present invention, the greater the benefits of the invention in terms of promoting uniform dosages of detergent from a package of particulate detergent or in a unit dosage which is formed into a tablet.
The processes of the invention may comprise the step of adding to the mixer a binder to facilitate production of the desired detergent particles. Generally such a binder will be liquid in the form of a solution or melt and will be added by spraying either directly into the mixer or onto the particulate components as they travel into the mixer. Preferably the binder is added directly into the mixer for example by spraying. The binder is added for purposes of enhancing agglomeration by providing a binding or sticking agent for detergent components. The binder may be any conventional detergent binding agent, preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrvlates, organic acids or their salts such as citric acid or citric salts. and mixtures thereof.
Other suitable binder materials includine those listed herein are described in Beerse et al, US
Patent number 5108646 (Procter and Gamble Company), the disclosure of which is incorporated herein by reference. The binder must be compatible with the detergent active particulate as will be appreciated by persons skilled in the an. Thus, where the stability of the detergent active particulate is adversely affected by water, the binder will be substantially water-free.
Thus, in one aspect of the invention, a first feed stream of detergent base powder is fed into the mixer and in addition a second feed stream comprising a detergent active particulates is fed into the mixer and binder is also present in the mixer. The binder may be fed directly via a third stream into the mixer or it may be contacted with the detergent base particles or detergent active particulates prior to one or both of these feed streams entering the mixer, for example the detergent active particulate (or a proportion of the base particles] may be entrained in the binder.
Where the mixer is divided into different zones, the three components may be fed into the same zone or optionally may be fed into different zones. In a preferred embodiment of the invention, the detergent base particles and detergent active particulates will be pre-mixed prior to addition of the binder.
In a further preferred aspect of the invention, after mixing of the detergent base particles and detergent active particulates, so that adhesion of the two components has taken place, a further liquid component is applied to the outside of the particles produced.
This further coating may be the same chemical composition as the binder or may be any of the other coating materials or detergent ingredients described below.
The moderate to low shear mixer to be used in the present invention may be for example a Lodige KM (trademark) (Ploughshare) moderate speed mixer, or mixer made by Fukae, Draes, Schugi or similar brand mixers which mix with only moderate to low shear. The Lodige KM
(ploughshare) moderate speed mixer which is a preferred mixer for use in the present invention comprises a horizontal hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached. Preferably, the shaft rotates at a speed of from about 1 S rpm to about 140 rpm, more preferably from about 80 rpm to about 120 rpm. The grinding or pulverizing is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm. Other mixers similar in nature which are suitable for use in the process include the Lodige PloughshareT"" mixer and the Drais~ K-T 160 mixer. Generally, in the processes of the present invention, the shear will be no greater than the shear produced by a Lodige KM mixer with the tip speed of the ploughs below 10 m/s, or even below 8mls or even lower.
Preferably, the mean residence time of the various starting detergent ingredients in the low or moderate speed mixer is preferably in range from about 0.1 minutes to about 30 minutes, most preferably the residence time is about 0.5 to about ~ minutes. In this way, the density of the resulting detergent agglomerates is at the desired level.
Other suitable mixers for use in the present invention are low or very low shear mixers such as rotating bowl agglomerators, drum agglomerators, pan agglomerators and fluid bed agglomerators.
Fluid bed agglomerators are particularly preferred. Typical fluidised bed agglomerators are operated at a superficial air velocity of from 0.1 to 4 m/s, either under positive or negative pressure. Inlet air temperatures generally range from -10 or 5°C up to 250°C. I-Iowever inlet air temperatures are generally below 200°C, or even below 150°C. The fluidized bed granulator is preferably operated such that the flux number FN of the fluid bed is at least about 2.~ to about 4.5. Flux number (FIvTm) is a ratio of the excess velocity (Ue) of the fluidisation gas and the particle density (pp) relative to the mass flux (q,;q) of the liquid sprayed into the bed at a normalized distance (D°) of the spraying device. The flux number provides an estimation of the operating parameters of a fluidized bed to control granulation within the bed.
The flux number may be expressed either as the mass flux as determined by the following formula:
FNm = log~oL {PaUe)/9nq~
or as the volume flux as determined by the formula:
FN,. = logio~{Ua/q~aq~
where q,,,;g is the volume of spray into the fluid bed. Calculation of the flux number and a description of its usefulness is fully described in WO 98/58046 the disclosure of which is herein incorporated by reference.
In addition, the fluidized bed is generally operated at a Stokes number of less than about 1, more preferably from about 0.1 to about 0.5. The Stokes number is a measure of particle coalescence for describing the degree of mixing occurring to particles in a piece of equipment such as the fluid bed. The Stokes number is measured by the formula:
Stokes number = 4pvd/9u wherein p is the apparent particle density, v is the excess velocity, d is the mean particle diameter and a is the viscosity of the binder. The Stokes number and a description of its usefulness is described in detail in ~'l'O 99/03964, the disclosure of which is herein incorporated by reference.
Thus, where the mixer is a fluid bed mixer, detergent base particles of the present invention are passed into a fluid bed optionally having multiple internal "stages" or "zones". A
stage or zone is any discrete area within the fluid bed, and these terms are used interchangeably herein. The process conditions within a stage may be different or similar to the other stages in the fluid bedldryer. It is understood that two adjacent fluid beds are equivalent to a single fluid bed having multiple stages. The various feed streams of detergent base particles and detergent active particulates can be added either at the same or at the different stages, depending on, for example, the particle size and moisture level of the feed stream. Feeding different streams to different stages can minimize the heat load on the fluid bed. and optimize the particle size and increase uniformity of the shape of the detergent particles produced.
The bed is typically fluidized with heated air in order to dry or partially dry moisture such as the binder liquids from the ingredients in the fluid bed. Where binder is sprayed into the fluid bed the spraying is generally achieved via nozzles capable of delivering a fine or atomized spray of the binder to achieve intimate nixing with the particulates.
Typically, the droplet size from the atomizer is less than about 2 times the particle size. This atomization can be achieved either through a conventional two-fluid nozzle with atomizing air, or alternatively by means of a conventional pressure nozzle. To achieve this type of atomization, the solution or slurry rheology is may have a viscosity of less than about 500 centipoise, preferably less than about 200 centipoise at the point of atomization. While the nozzle location in the fluid bed may be in most any location, the preferred location is a positioning that allows a vertical down spray of any liquid components such as binder. This may be achieved for example, using a top spray configuration. To achieve best results, the nozzle location is placed at or above the f7uidized height of the particles in the fluid bed. The fluidized height is typically determined by a weir or overflow gate height. The agglomeration/granulation zone of the fluid bed may be followed by an optional coating zone, followed by a drying zone and a cooling zone. Of course, one of ordinary skill in the art will recognize that alternative arrangements are also possible to achieve the resultant particles of the present invention.
Typical conditions within a fluid bed apparatus of the present invention include: (i) a mean residence time from about 1 to about 20 minutes, (ii) a depth of unfluidised bed of from about 100 to about 600 mm, (iii) a droplet spray size of less than 2 times the mean particle size in the bed, which is preferably not more than about 100 micron more preferably not more than 50 microns, (iv) spray height generally from 150 to 1600 mm of spray height from the fluid bed plate or preferably 0 to 600mm from the top of the fluid bed , (v) from about O.l to about 4.0 m/s.
preferably 1.0 to 3.Orrvs of f7uidizing velocity and (vi) from about 12 to about 200 °C of bed temperature, preferably 15 to 100°C. Once again. one of ordinary skill in the art will recognise that the conditions in the fluid bed may vary depending on a number of factors.
The detergent particles produced in the mixer can be further processed by adding a coating agent to improve the particle colour, increase the particle whiteness or improve the particle flowability after the detergent particles exit the mixer or the dryer if an optional drying step is added subsequently to the mixer or in a later stage in the mixer, to obtain the high density granular detergent compositions produced by the processes of the invention.
Those skilled in the art will appreciate that a wide variety of methods may be used to dry as well as cool the exiting detergent without departing from the scope of the invention. Since the mixer can be operated at relatively low temperatures, the need for cooling apparatus is generally not required in the present process which thereby further reduces manufacturing costs of the final product.
Another optional processing step includes continuously adding a coating agent such as zeolite and/or fumed silica to the mixer to facilitate free f7owabiliy of the resulting detergent particles and to prevent over agglomeration. Such coating agents generally have a mean particle size below 100 microns, preferably below 60 microns, even more preferably below 50 microns.
Any coating stage may take place either immediately after formation of the detergent particles of the invention either before or after any drying step and optionally after the detergent particles have been mixed with additional detergent ingredients for forming a fully formulated detegent composition. Preferably any such coating agent will also have detergent active properties. A particularly preferred coating agent is a surfactant or aqueous solution of surfactant.
Detergent ingredients which are suitable as ingredients of the base powder, and/or as ingredients of the detergent active particulates and/or as ingredients of any additional ingredients added to the detergent particles of the present invention to form the fully formulated detergent compositions of the invention are described below.
Deter eg nt Ingredients Surfactant Suitable surfactants for use in the invention are anionic, nonionic, ampholytic, and zwitterionic classes of these surfactants, is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S.P. 4.259,217 issued to Murphy on March 31, 1981.
Preferably. the detergent particle of the present invention and compositions comprising such particles comprises an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition.
These can include salts (including, for example, sodium, potassium, ammonium. and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.
The anionic surfactants may be present in the detergent particle in amounts below 25 w or even below 20 wrt % but in a final detergent composition comprising the particle, is preferably present at a level of from 0.1 % to 60%. more preferably from 1 to 40%, most preferably from 5% to 30% by weight.
Other anionic surfactants include the anionic carboxylate surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxvlates and soaps ("allyl carboxyls") such as water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-I-octanoic acid and 2-pentyl-I-heptanoic acid. Certain soaps may also be included as suds suppressors. Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R1) CH2 COOM, wherein R is a CS-C I ~ linear or branched alkyl or alkenyl group, R 1 is a C I -C4 alkyl group and M is an alkali metal ion. Other anionic surfactants include isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the CS-CIA acyl-N-(CI-C4 alkyl) and -N-(CI-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein). Alkyl sulfate surfactants are preferably selected from the linear and branched primary CI0-CI g alkyl sulfates, more preferably the CI I-CIS branched chain alkyl sulfates and the CIA-C14 linear chain alkyl sulfates. Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C10-C 18 allyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the allyl ethoxvsulfate surfactant is a C11-Clg, most preferably C11-CI5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5.
moles of ethylene oxide per molecule.
Preferred surfactant combinations are mixtures of the preferred alkyl sulfate and/ or sulfonate and alkyl ethoxysulfate surfactants optionally with cationic surfactant. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids. alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Essentially any alkoxvlated nonionic surfactant or mixture is suitable herein.
The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are particularly suitable for use herein.
Particularly preferred are the condensation products of straight or branched, primary or secondary alcohols having an alkyl group containing from 6 to 22 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONRIZ wherein : RI is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl: and R2 is a C5-C31 hydrocarbyl;
and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Suitable alkylpolysaccharides for use herein are disclosed in LT.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units. Preferred alkylpolyglycosides have the formula:
R2O(CnH2n0)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3(OR4)xN0(RS)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are CIO-Clg alkyl dimethylamine oxide, and CIO-18 acylamido alkyl dimethylamine oxide.
Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds.
Betaines such as C12-18 dimethyl-ammonio hexanoate and the CIO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines and sultaine surfactants are exemplary 2witterionic surfactants for use herein.
Suitable cationic surfactants to be used herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono C6-C16, preferably C6-Cl0 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Cationic ester surfactants such as choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529 are also suitable as are cationic mono-alkoxylated amine surfactants preferably of the general formula I:
R' /((CH2)2-a0)~-tH
N+ /
CH3/ \CH3 wherein R 1 is C 10-C 1 g hydrocarbyl and mixtures thereof, especially C 10-C
14 alkyl, preferably C10 and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide. The levels of the cationic mono-alkoxylated amine surfactants in the detergent compositions of the invention are generally from 0.1 % to 20%, preferably from 0.2% to 7°io, most preferably from 0.3% to 3.0% by weight.
Cationic bis-alkoxvlated amine surfactant such as +/CH~CH20H
X
CH / \CH2CH20H
are also useful, wherein R1 is C10-Clg hydrocarbyl and mixtures thereof, preferably C10, C12 C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride.
Bleach Activator The detergent particles or detergent compositions containing them preferably comprise a bleach activator, preferably comprising an organic peroxyacid bleach precursor. It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxy acid bleach precursor, as defined herein. The production of the organic peroxyacid occurs then by an in situ reaction of the precursor with a source of hydrogen peroxide. The bleach activator may alternatively, or in addition comprise a preformed peroxy acid bleach.
It is preferred that the bleach activator is present in the detergent particle. It may be preferred that the bleach activator is present as a separate, admixed particle. Preferred hydrophobic peroxy acid bleach precursor preferably comprise a compound having an oxy-benzene sulphonate group, preferably NOBS, DOBS, LOBS and/ or NACA-OBS.
Preferred hydrophilic peroxy acid bleach precursors preferably comprises TAED.
Peroxyacid Bleach Precursor Peroxvacid bleach precursors are compounds which react with hydrogen peroxide in a perhvdrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as O
X-C-L
where L is a leaving group and X is essentially any functionality. such that on perhydroloysis the structure of the peroxyacid produced is O
X-C-OOH
For the purpose of the invention, hydrophobic peroxyacid bleach precursors produce a peroxy acid of the formula above wherein X is a group comprising at least 6 carbon atoms and a hydrophilic peroxyacid bleach precursor produces a peroxvacid bleach of the formula above wherein X is a group comprising 1 to 5 carbon atoms.
The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition. Preferred L groups are selected from the group consisting of:
Y R3 RsY
-O ~ , -O U Y , and -O
-N-C-R -N N -N-C-CH-R
I ' , I I
R3 ~ R3 Y
I
Y
-O-C H=C-C H=C H2 -O-C H=C-C H=C H2 , O Y O
-NCH2-C\NR4 _N~ ~NR4 -~C-R ~C/ , ' II
O
-O-C=CHR4 , and -N-S-CH-R4 and mixtures thereof, wherein RI is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group. Any of R1, R3 and R4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
The preferred solubilizing groups are -S03 M+, -C02 M+, -S04 M+, -N+(R3)4X and O<--N(R3)3 and most preferably -S03 M+ and -C02 M+ wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a canon which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
Preferably, M is an alkali metal, ammonium or substituted ammonium canon, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
Peroxyacid bleach precursor compounds are preferably present in final detergent compositions at a level of from 0.5% to 30% by weight, more preferably from 1 % to 15% by weight, most preferably from 1.5% to 10% by weight. The ratio of hydrophilic to hydrophobic bleach precursors, when present, is preferably from 10:1 to 1:10, more preferably from 5;1 to 1:5 or even from 3:1 to 1:3. Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
Allyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide t'~pe include the N-,IvT,IvTINI
tetra acet<~lated alkylene diamines wherein the all.~~lene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains I, 2 and 6 carbon atoms.
Tetraacetyl ethylene diamine (TAED) is particularly preferred as hydrophilic peroxy acid bleach precursor.
Other preferred alkyl percarboxvlic acid precursors include sodium 3,5.5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (HOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
R~ -CNR2C-L R~ NCR2CL
O R5 O or R5 O O
wherein R1 is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R5 is H
or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. RI preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. RI may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, aryl, wherein said RZ may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
RS is preferably H
or methyl. R1 and R5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It can be preferred that RI and RS forms together with the nitrogen and carbon atom a ring structure.
Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- sulfonate, and the highly preferred (6-nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A-0170386.
Perbenzoic acid precursor compounds which provide perbenzoic acid on perhydrolysis benzoxazin organic peroxyacid precursors, as disclosed for example in EP-A-332294 and EP-A-482807 and cationic peroxvacid precursor compounds which produce cationic peroxyacids on perhydrolysis are also suitable. Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127.82: 5.093,022;
5,106,528; U.K.
1,382.594: EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxvacid precursors are described in UK
Patent Application No. 9407944.9 and US Patent Application Nos. 08!298903, 08/298650, 08; 298904 and 08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
The particles or compositions of the present invention may contain, in addition to, or as an alternative to an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 0.1% to 15% by weight, more preferably from 1% to 10% by weight. A preferred class of organic peroxyacid compounds are the amide substituted compounds as described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxvtetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
Peroxide Source Inorganic persalts are a preferred source of peroxide. Preferably these salts are present at a level of from 0.01% to 50% by weight, more preferably of from 0.5% to 30% by weight of the particle or composition of the invention. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.
Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB02H202 or the tetrahydrate NaB02H202.3H20.
Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03.3H202, and is available commercially as a crystalline solid. Potassium peroxymonopersulfate is another inorganic perhydrate salt suitable for use herein.
Chelants As used herein, chelants refers to detergent ingredients which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacit)~, but preferably selectively bind heave metal ions such as iron, manganese and copper.
Chelants are generally present in the detergent particle or final detergent composition at a level of from 0.005% to 10%, preferably from 0.1% to 5°0, more preferably from 0.25% to 7.5%
and most preferably from 0.3% to 2% by weight of the compositions or component Suitable chelants include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates, preferably, diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylene phosphonic acid.
Other suitable chelants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof, and iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516.102 are also suitable herein. The ~-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable. EP-A-476.257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen.
keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant.
Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are alos suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine-N.N'-disuccinic acid (EDDS) and 1,l hvdroxyethane diphosphonic acid or the alkali metal, alkaline earth metal.
ammonium, or substituted ammonium salts thereof, or mixtures thereof. In particular the chelating agents comprising a amino or amine group can be bleach-sensitive and are suitable in the compositions of the invention.
Water-Soluble Builder Compound The component or compositions herein preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1 %
to 80% by weight, preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight.
The detergent compositions of the invention may comprise phosphate-containing builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8°~o to 40%. The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, malefic acid, diglycolic acid, tartaric acid, tarnonic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxvsuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1.398,422 and in U.S.
Patent No. 3,936.448, and the sulfonated pyrolysed citrates described in British Patent No.
1,439.000. Preferred polycarboxylates are hydroxy carboxylates containing up to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
Borate builders and builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolvphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate. sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Examples of organic polymeric compounds include the water soluble organic homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with malefic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Partially Soluble or Insoluble Builder Compound The panicles or detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight. Examples of largely water insoluble builders include the sodium aluminosilicates.
As mentioned above, it may be preferred in one embodiment of the invention, that only small amounts of alumino silicate builder are present.
Suitable aluminosilicate zeolites have the unit cell formula Naz[(A102)z(Si02)y]. x120 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite .A, Zeolite B, Zeolite P. Zeolite X. Zeolite HS and mixtures thereof. Zeolite A has the formula:
Na 12 [A102) 12 (Si02)12~. xH20 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nag6 [(A102)g6(Si02)106~~
276 H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
The zeolite MAP can be present at a level of from 1 % to 80%, more preferably from 15%
to 40% by weight. Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2. Of particular interest is zeolite MAP
having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a median particle size d50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres. The d50 value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer, described herein. Other methods of establishing d50 values are disclosed in EP 384070A.
Other Deter eg nt Ingredients A preferred ingredients of the compositions herein are dyes and dyed particles or speckles, which can be bleach-sensitive. The dye as used herein can be a dye stuff or an aqueous or nonaqueous solution of a dye stuff. It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the detergent particles or speckles, preferably such that levels of dye solution are obtained up to 2% by weight of the dyed particle.
or more preferably up to 0.5% by weight, as described above. The dye may also be mixed with a non-aqueous carrier material, such as non-aquous liquid materials including nonionic surfactants.
Optionally, the dye also comprising other ingredients such as organic binder materials, which may also be a non-aqueous liquid.
The dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs include E104 - food yellow 13 (quinoline yellow), E110 - food yellow 3 (sunset yellow FCF), E131 -food blue 5 (patent blue V), Ultra Marine blue (trade name), E133 - food blue 2 (brilliant blue FCF), E140 - natural green 3 (chlorophyll and chlorphyllins), E141 and Pigment green 7 (chlorinated Cu phthalocyanine). Preferred dyestuffs may be Monastral Blue BV
paste (trade name) and,% or Pigmasol Green (trade name).
Another preferred ingredient of the particles or compositions of the invention is a perfume or perfume composition. Any perfume composition can be used herein.
The perfumes may also be encapsulated. Preferred perfumes containing at least one component with a low molecular weight volatile component , e.g. having a molecular weight of from 150 to 450 or preferably 350. Preferably, the perfume component comprises an oxygen-containing functional group. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.
Another highly preferred ingredient useful in the particles or compositions herein is one or more additional enzymes. Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
Preferred enzymes are discussed above with respect to the detergent active particulates.
The same enzymes are preferred as components of the detergent base powder or as additional detergent ingredients added to the detergent particles of the invention to form a fully formulated detergent.
The detergent particles or compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, preferably as a detergent active particulate component as mentioned above. Examples are commercially marketed by Ciba Geigy Corporation as Tinopal-LTNPA-GXT"' and Tinopal-CBS-XTM.
Others include Tinopal 5BM-GXT"', Tinopal-DMS-XT"' and Tinopal AMS-GXTM by Ciba Geigy Corporation.
Photo-Bleachine Agent As described above, photo-bleaching agents are preferred ingredients of the compositions and are preferably present in the form of the detergent active particulates as discussed above.
However, they may optionally be present in the detergent base particles or as additional detergent ingredients for addition to the detergent particles of the invention for forming the fully formulated detergnet compositions of the invention.
Oreanic Polymeric lnQredients Organic polymeric compounds are preferred additional herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. Bv organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quaternised ethoxylated (poly) amine clay-soil removali anti-redeposition agent in accord with the invention.
Organic polymeric compound is typically incorporated in the finished detergent compositions of the invention at a level of from 0.01°~o to 30%, preferably from 0.1°~o to 15%, most preferably from 0.5% to 10% by v~~eight of the compositions or component.
Terpolymers containing monomer units selected from malefic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000. are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U.S. Patent 4,968,451, Scheibel et al., and U.S. Patent 5,415,807, Gosselink et al., and in particular according to US application no.60/051517.
Another organic compound, which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
H3 ~ H3 X-~OCH2CH2)n i +-CH2-CH2~-CH2)a N+-CH2CH~0-~X
b (CH2CH20 ~ X (CH2CH20 ~ X
wherein X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0: for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35: for cationic diamines (b=1), n is at least about 12 with a typical range of from about 12 to about 42.
Other dispersantsi anti-redeposition acents for use herein are described in EP-and US 4,659,80? and US 4.664,848.
Suds Suppressin System The suds supressing system is preferably also present in the form of the detergent active particulates as described above. Such components may however be present in the detergent base particles or as additional detergent ingredients for addition to the detergent particles of the invention for formulating a finished detergent composition.
Polymeric dye transfer inhibiting agents may also be present in the detergent particles or compositions of the invention. When present they are generally in amounts from 0.01 % to 10 %, preferably from 0.05% to 0.5% based on the final detergent compositions and are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolvmers or combinations thereof, whereby these polymers can be cross-linked polymers.
Polymeric soil release agents, which are described above are also preferably present as detergent active particulates. However they may be present alternatively or in addition, in the detergent base particles or as additional detergent ingredients for addition to the detergent particles of the invention for formulating a finished detergent composition.
Other optional ingredients suitable for inclusion in the compositions of the invention include colours and filler salts, with sodium sulfate being a preferred filler salt.
Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. Also, preferably combined with a carbonate salt, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides and dyes, such as those described in US Patent 4.285,841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference), can be present.
The detergent compositions can include as an additional component a chlorine-based bleach. However, since the detergent.compositions of the invention are solid, most liquid chlorine-based bleaching will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable. Alternatively, a chlorine based bleach can be added to the detergent composition by the user at the beginning or during the washing process.
The chlorine-based bleach is such that a hypochlorite species is formed in aqueous solution. The hypochlorite ion is chemically represented by the formula OCI-.
Those bleaching agents which yield a hypochlorite species in aqueous solution include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides. Specific examples include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-~.5-dimethylhydantoin. N-chlorosulfamide, Chloramine T, Dichloramine T. chloramine B and Dichloramine B. A preferred bleaching agent for use in the compositions of the instant invention is sodium hypochlorite, potassium hypochlorite, or a mixture thereof. A preferred chlorine-based bleach can be Triclosan (trade name).
Most of the above-described hypochlorite-yielding bleaching agents are available in solid or concentrated form and are dissolved in water during preparation of the compositions of the instant invention. Some of the above materials are available as aqueous solutions.
Laundry Washine Method Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from l Og to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
Preferred washing machines may be the so-called low-fill machines.
In a preferred use aspect the composition is forntulated such that it is suitable for hard-surface cleaning or hand washing. In another preferred aspect the detergent composition is a pre-treatment or soaking composition, to be used to pre-treat or soak soiled and stained fabrics.
Examples Abbreviations used in the Examples In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS : Sodium linear C11-13 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate branched AS . branched Sodium alkyl sulfate as described in W099/19454 CxyAS . Sodium C 1 x - C 1 y alkyl sulfate C46SAS . Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS : Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide CxyEz : C 1 x-C 1 y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS : R2.N+(CH3)2(C2H40H) with R2 = C12 - C14 QAS 1 : R2.N+(CH3)2(C2H40H) with R2 = C8 - C 11 APA : C8 - C10 amido propyl dimethyl amine Soap : Sodium linear alkyl carboxylate derived from an 80.!20 mixture of tallow and coconut fatty acids STS : Sodium toluene sulphonate CFAA : C12-Cl4 (coco) alkyl N-methyl glucamide TFAA . C16-C18 alkyl N-methyl glucamide TPKFA : C 12-C 14 topped whole cut fatty acids STPP . Anhydrous sodium tripolyphosphate TSPP . Tetrasodium pyrophosphate Zeolite A : Hydrated sodium aluminosilicate of formula Nal2(AlO2Si02)12.27H20 having a primary panicle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis) NaSKS-6 : Crystalline layered silicate of formula d-Na2Si205 Citric acid . Anhydrous citric acid Borate : Sodium borate Carbonate . Anvdrous sodium carbonate with a particle size between 200~m and 900pm Bicarbonate . Anhydrous sodium bicarbonate with a particle size distribution between 400pm and 1200pm Silicate : Amorphous sodium silicate (Si02:Na20 = 2.0:1 ) Sulfate : Anhydrous sodium sulfate Mg sulfate . Anhydrous magnesium sulfate Citrate . Tri-sodium citrate dehydrate of activity 86.4%
with a particle size distribution between 425pm and 850~m MA/AA : Copolymer of 1:4 maleic/acrylic acid, average m. W. about 70,000 MA/AA ( 1 ) . Copolymer of 4:6 maleic/acrylic acid, average m. W. about 10,000 AA . Sodium polyacrylate polymer of average molecular weight 4,500 CMC : Sodium carboxymethyl cellulose Cellulose ether l cellulose ether with a degree of polymerization :Methy of 650 available from Shin Etsu Chemicals Protease . Proteolytic enzyme, having 3.3/o by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Protease I : Proteoh~tic enzyme. having 4% by weight of active enzyme, as described in VSO 95/10591. sold by Genencor Int. lnc.
Alcalase : Proteolvtic enzyme, having 5.3% by weight of active enzyme. sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase : Amylolyic enzyme, having I .6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T
Lipase : Lipolytic enzyme, having 2.0% by weight of active enzyme. sold by NOVO Industries A/S under the tradename Lipolase Lipase (1) : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra Endolase : Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaB02.3H2 O.H2O2-PB1 . Anhydrous sodium perborate bleach of nominal formula NaB02.H 2O2 Percarbonate . Sodium percarbonate of nominal formula 2Na2C03.3H2O2 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt NAC-OBS : (6-nonamidocaproyl) oxybenzene sulfonate TAED : Tetraacetylethylenediamine DTPA . Diethylene triamine pentaacetic acid DTPMP . Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename bequest 2060 EDDS . Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer sodium salt.
Photoactivated : Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer Photoactivated :Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate HEDP : 1,1-hydroxyethane diphosphonic acid PEGx . Polyethylene glycol, with a molecular weight of x (typically 4,000) PEO : Polyethylene oxide, with an average molecular weight of 50,000 TEPAE : Tetraethylenepentaamine ethoxylate PVI . Polwinvl imidosole, with an average molecular weight of 20.000 PVP : Polyvinylpvrolidone polymer, with an average molecular weight of 60,000 PVNO . Polyvinylpvridine N-oxide polymer. with an average molecular weight of 50,000 PVPVI : Copolymer of polvvinylpvrolidone and vinylimidazole, with an average molecular weight of 20,000 QEA : bis((C2H50)(C2H40)n)(CH3) -N+-C6H12-N+-(CH3) bis((C2H50)-(C2H4 O))n, wherein n = from 20 to 30 SRP 1 . Anionically end capped poly esters SRP 2 : Diethoxylated poly (1, 2 propylene terephtalate) short block polymer PEI . Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Silicone antifoam:Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1 Opacifier . Water based monostyrene latex mixture, sold by BASF
Aktiengesellschaft under the tradename Lytron Wax : Paraffin wax HMSO . hexamethylene diamine tetra(ethylene oxide)24 The following are examples of the present invention.
EXAMPLE I
This Example illustrates a process according to this invention which produces uniform free flowing, good dispensing and dissolving detergent particles with uniformity of colour and particle shape. Multiple detergent starting ingredients are dry mixed in an orbital vertical screw mixer of 200kg batch size, and several batches prepared. This bulk premix is added into a horizontal rotating drum type mixer with internal baffles - a laboratory scale example having batch size 40kg. A proportion of premix is sampled and added to the mixer. The smaller particles which pose a segregation risk are dry mixed into the mixer.
Binding agent, C45AE7, is sprayed into the mixer using an air atomised nozzle.
The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further 1 minute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % ~'~'eight of Total Feed Drv materials added to the~remix Detergent premix* 98.48%
Photobleach 0.02°ro Perfume encaps type 1 0.5%
Perfume encaps type 2 0.2%
Binding agent C45AE7 alcohol ethoxylate 0.7%
Anti-caking agent Zeolite A 0.1 * = comprising of sodium linear alkyl benzene sulphonate ( 13.4wrt%), zeolite A (40°~0), sodium sulphate (23.5%), sodium carbonate (8.4%), magnesium sulphate (0.7wt%), EDDS
(0.4wt%), MA/AA (2.Swt%), soap (l.Swt%), QAS l(2.Owt%), HEDP (0.3wt%), optical brightener (O.Swt%), water (5.3wt%), diamine hexamethylene tetra (ethylene oxide) 24 (l.5wt%).
EXAMPLE II
This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in example 1, of composition as listed below. A proportion of premix is sampled and added to the mixer.
Binding agent, C45AE7 mixed with PEG 4000, is sprayed into the mixer using an air atomised nozzle. The premix of increased cohesivity is left to mix for 1 minute. The smaller particles which pose a segregation risk are dry mixed into the mixer. The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further 1 minute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % Weight of Total Feed Dry materials added to the premix Detergent premix* 98.48%
Photobleach 0.02%
Perfume encaps type 1 0.5%
Perfume encaps type 2 0.2%
Bindine agent C45AE7 alcohol ethoxvlate 1.0%
PEG4000 0.5%
Anti-caking a Zeolite A 0.2%
EXAMPLE III
This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in example I, of composition as listed below. A proportion of premix is sampled and added to the mixer.
Binding agent, C45AE5, is sprayed into the mixer using an air atomised nozzle. The premix of increased cohesivity is left to mix for I minute. The smaller particles which pose a segregation risk are dry mixed into the mixer. The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further 15 seconds. The product is run into a storage box.
Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % Weight of Total Feed Dry materials added to the premix Detergent premix* 97.78%
Photobleach 0.02%
Perfume encaps type 1 0.4%
Perfume encaps type 2 0.1 Binding aft C45AE5 alcohol ethoxylate 1.5%
Anti-cakin~agent Zeolite A 0.2%
EXAMPLE IV
This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in example 1, of composition as listed below. A proportion of premix is sampled and added to the mixer.
Bonding agent, C45AE7, is sprayed into the mixer using an air atomised nozzle. The premix of increased cohesivity is left to mix for 1 minute. The smaller particles which pose a segregation risk are dry mixed into the mixer. A further spray-on of bonding agent is applied to fix the small particles firmly to the surface of the larger host particles. The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further I
minute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % Weight of Total Feed Drv materials added to the_premix Detergent premix* 98.2%
Photobleach 0.02%
Perfume encaps type 1 0.5%
Perfume encaps type 2 0.2%
Binding fluid C45AE7 alcohol ethoxylate 1.0%
Anti-caking agent Zeolite A 0.08°~0 EXAWPLE V
This Example also illustrates the process of the invention and incorporates the parameters of Example I. A premix of dry detergent materials is prepared as in example 1, of composition as listed below. A proportion of premix is sampled and added to the mixer.
The fine segregatable particles are dispersed into a carrier fluid such as C45AE7 in a tank, using low shear agitation, mixed for 10 minutes. The suspension of fine particles in fluid is pumped to a spray nozzle and atomised onto the premix particles in the mixer.
The product is left to mix for 2 minutes and anti-caking agent (zeolite A) is added into the mixer and mixed for a further 1 minute. The product is run into a storage box. Other detergent additives such as enzymes, percarbonate and dyed carbonate speckles are post-added in a mixing step with other liquid additives such as perfume, to form the final detergent.
Component % Weight of Total Feed Drv materials added to the premix Detergent premix* 96.48%
Photobleach 0.02%
Binding fluid C45AE7 alcohol ethoxylate 3.0%
Anti-caking agent Zeolite A 0.5%
Further example compositions In the following examples all levels are quoted as % by weight of the full finished detergent composition:
TABLE
The following compositions are in accordance with the invention.
A B C D E F ParticleSpan E Sphericity ize Colour(Mean) (median, ifferenc Vim) of raw material compare to finished compositi n 1. S ra 50qm 1.8 .4 1.9 -dried ranules LAS .0 .0 11.0 .0 .0 .0 AS 1.0 C45AS 1.0 1.0 C16-C17 .0 .0 .0 branched S
DTPA, .5 .6 0.5 .7 1.0 .5 HEDP
nd/or EDDS
MgS04 .5 .4 .5 .4 .5 .5 Sodium 10.0 .0 .0 .0 .0 10.0 arbonate Sodium .0 .0 .0 5.0 .0 .0 ulphate eolite 18.0 0.0 18.0 10.0 0.0 17.0 A
IMA/AA or 1.0 1.5 1.0 .6 1.0 0.6 (QAS 1 1.0 0.5 1.0 .8 1.0 Brightener 0.1 0.05 .05 0.06 0.05 0.05 IHMEO 0.5 .5 1.0 .5 1.0 1.0 I
ISoap 1.5 1.0 1.5 1.5 (Component is within the ~i remix (Spray dried50.0 50.0 8.0 0.0 0.0 50.0 I
~granules (1 ) (Nonionic 5.0 Sodium .0 .0 .0 .0 5.0 OO~m 1.5 .0 1.5 carbonate Sodium .0 1.0 350~m 1.6 .5 1.5 ulphate QAS 1 .0 1.0 500~m .7 .0 .1 gglomerate Nonionic 10.0 500~m 1.9 .3 1.8 gglomerate SKS-6 / 12.0 350pm 1.8 14.6 1.9 LAS
gglomerate Silicone .5 .5 .0 .5 .5 500~m .0 14.3 1.5 ntifoam gglomerate SRP 1 ,5 ~ .5 .3 500~m .0 10.4 .0 AED .5 .5 .0 550~m .5 11.4 .6 ggiomerate SKS-6 3.5 3.5 9.0 3.5 5.0 O~m 1.9 6.0 1.7 powder AED 1.5 .0 80~m 1.7 9.5 1.6 powder Premix binder pplied to he premix (2) PEG 4000 5.0 PEG 1500 .0 S, LAS, 5.0 .0 MBAS
ater as 10.0 15.0 binder (removed on vying) Other additives os t-added to make the final detergent formulation . S ra -on materials Pertume .4 .2 .4 .4 .5 .3 WO 00!78908 PC'T/US00/16916 ..
5. D
added materials Premix 0.0 5.0 55.0 65.0 0.0 0.0 (2) Enzymes .0 1.5 1.0 1.3 1.2 1.5 (protease, lipolase, mylase, cellulase) NACAOBS 3.0 .5 .0 3.5 3.5 .5 Sodium 13.0 10.0 10.0 12.0 12.0 10.0 percarbonat Photobfeach0.02 0.02 .02 0.02 0.02 0.02 Perfume .7 .5 .6 .8 .9 .4 ncapsulate Citric .0 .0 .0 .0 .5 .0 acid Sodium 1.0 1.0 1.0 .5 1.5 1.5 rbonate peckle eolite .1 .3 A
AED .p gglomerate Silicone .0 ntifoam ggiomerate . Coatin pplied to premix (2) Burkeite .0 5.0 8.0 5.0 (applied in 30wt%
queous olution) Brightener .1 .1 Fillers up to 100%
Finished product Median OOpm OOpm OO~m 800~m800pmOOp.m particle size Span 1.4 1.2 1.4 1.2 1.4 1.6 (geometric tandard eviation) Roundness 1.30 1.20 1.35 1.40 1.45 1.40 (mean) hiteness 98.0 6.5 98.5 92.0 97.0 101.5 ~IW=L-3b Having thus described the invention in detail, it will be obvious to those skilled in the an that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.
Claims (15)
1. A method for making a detergent particle comprising selecting detergent base particles having a geometric mean particle size from 500 - 2500 microns and, in a moderate to low shear mixing step, adhering detergent active particulates to the detergent base particles, the detergent active particulates having a geometric mean particle diameter no greater than 40% of the geometric mean particle diameter of the detergent base particles and comprising a detergent active selected from perfumes, enzymes, photobleaches, catalysts, soil release polymers, suds suppressors, bleaching compound, whitening agents and layered silicates.
2. A method according to claim 1 in which the geometric mean particle diameter of the detergent active particulates is below 200µm.
3. A method for making a detergent composition according to claim 1 or claim 2 in which a first stream of detergent base particles is added to the mixer; a second stream comprising the detergent active particulates is added to the mixer and binder also present in the mixer effects adhesion of the detergent active particulates to the detergent base particles.
4. A method according to claim 3 in which the binder is added by a third stream directly into the mixer.
5. A method according to any preceding claim in which a binder is added to the detergent base particles or the detergent active particulate prior to their addition to the mixer.
6. A method according to any preceding claim in which the geometric mean particle diameter of the detergent active particulate is no greater than 20% of the geometric mean particle diameter of the detergent base particles.
7. A method according to any preceding claim in which the geometric mean particle diameter of the detergent active particulates is no greater than 10% of the geometric mean particle diameter of the detergent base particles.
8. A detergent composition according to any preceding claim in which the geometric mean particle diameter of the detergent active particulates is no greater than 5% of the geometric mean particle diameter of the detergent base particles.
9. A method according to any preceding claim in which the detergent active particulates comprise photobleach.
10. A method according to any preceding claim in which the detergent active particulates comprise solid particles comprising perfume.
11. A method according to any preceding claim in which the geometric mean particle diameter of the detergent active particulates is no greater than 150 microns.
12. A method according to any preceding claim in which the low shear mixer comprises a rotating drum mixer.
13. A method according to any preceding claim in which the detergent base particles comprise agglomerates, particulate detergent raw materials, spray dried powders or mixtures thereof.
14. A detergent particle obtainable by a method according to any preceding claim.
15. A detergent composition comprising detergent particles according to claim 14.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14009499P | 1999-06-21 | 1999-06-21 | |
US60/140,094 | 1999-06-21 | ||
PCT/US2000/016916 WO2000078908A1 (en) | 1999-06-21 | 2000-06-20 | Detergent particles and processes for making them |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2375408A1 true CA2375408A1 (en) | 2000-12-28 |
Family
ID=22489731
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002375408A Abandoned CA2375408A1 (en) | 1999-06-21 | 2000-06-20 | Detergent particles and processes for making them |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1187900A1 (en) |
JP (1) | JP2003503545A (en) |
CN (1) | CN1181175C (en) |
AR (1) | AR024429A1 (en) |
AU (1) | AU5625700A (en) |
BR (1) | BR0011836B1 (en) |
CA (1) | CA2375408A1 (en) |
MX (1) | MXPA02000060A (en) |
WO (1) | WO2000078908A1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050181969A1 (en) * | 2004-02-13 | 2005-08-18 | Mort Paul R.Iii | Active containing delivery particle |
DE102005036346A1 (en) * | 2005-07-29 | 2007-02-01 | Henkel Kgaa | Granulates/agglomerate for detergents or cleaning agents comprises dust portion content from the elutriation method, surfactant content, and nuclear particle |
EP2007867A2 (en) * | 2006-04-20 | 2008-12-31 | The Procter and Gamble Company | Flowable particulates |
BRPI0603808A2 (en) * | 2006-04-20 | 2009-03-10 | Procter & Gamble | release particle containing active |
EP1918362A1 (en) * | 2006-10-16 | 2008-05-07 | The Procter & Gamble Company | Low builder, highly water-soluble, low-density solid laundry detergent composition |
CN105886137A (en) * | 2014-12-15 | 2016-08-24 | 上海和黄白猫有限公司 | High-density low temperature quickly dissolved washing powder and preparation method thereof |
US10543464B2 (en) * | 2015-02-10 | 2020-01-28 | Novozymes A/S | Method for mixing of particles |
EP4247930A1 (en) * | 2020-11-19 | 2023-09-27 | The Procter & Gamble Company | Method of making detergent compositions comprising perfume |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2044536A1 (en) * | 1969-09-24 | 1971-04-08 | Colgate Palmolive Co , New York, NY (V St A ) | Process for the production of an enzyme-containing granulate for washing purposes |
FR2285453A1 (en) * | 1974-09-23 | 1976-04-16 | Colgate Palmolive Co | Low foaming detergent compsns - prepd. by mixing polyorgano siloxane with anionic and non ionic detergents and auxiliary detergent salt |
NZ203689A (en) * | 1982-04-15 | 1985-11-08 | Colgate Palmolive Co | Particulate fabric-softening detergent compositions |
GB2190921A (en) * | 1986-05-27 | 1987-12-02 | Unilever Plc | Granular detergent composition |
DE4243704A1 (en) * | 1992-12-23 | 1994-06-30 | Henkel Kgaa | Granular detergents and / or cleaning agents |
HUP0103664A3 (en) * | 1998-09-25 | 2003-04-28 | Procter & Gamble | Granular detergent composition |
-
2000
- 2000-06-20 JP JP2001505653A patent/JP2003503545A/en not_active Withdrawn
- 2000-06-20 BR BRPI0011836-2A patent/BR0011836B1/en not_active IP Right Cessation
- 2000-06-20 EP EP00941565A patent/EP1187900A1/en not_active Withdrawn
- 2000-06-20 AU AU56257/00A patent/AU5625700A/en not_active Abandoned
- 2000-06-20 CA CA002375408A patent/CA2375408A1/en not_active Abandoned
- 2000-06-20 WO PCT/US2000/016916 patent/WO2000078908A1/en not_active Application Discontinuation
- 2000-06-20 CN CNB008118728A patent/CN1181175C/en not_active Expired - Fee Related
- 2000-06-20 MX MXPA02000060A patent/MXPA02000060A/en active IP Right Grant
- 2000-06-21 AR ARP000103096 patent/AR024429A1/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
CN1181175C (en) | 2004-12-22 |
EP1187900A1 (en) | 2002-03-20 |
JP2003503545A (en) | 2003-01-28 |
BR0011836A (en) | 2002-03-05 |
MXPA02000060A (en) | 2002-07-02 |
WO2000078908A1 (en) | 2000-12-28 |
AU5625700A (en) | 2001-01-09 |
BR0011836B1 (en) | 2012-06-12 |
AR024429A1 (en) | 2002-10-02 |
CN1375001A (en) | 2002-10-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6583098B1 (en) | Detergent composition | |
CA2352627C (en) | Effervescence components | |
US6683043B1 (en) | Process for manufacturing effervescence components | |
US6579844B1 (en) | Detergent particles and methods for making them | |
CA2375408A1 (en) | Detergent particles and processes for making them | |
US6833346B1 (en) | Process for making detergent particulates | |
CA2386338A1 (en) | Detergent compositions and methods for cleaning | |
WO2000024859A1 (en) | Detergent particles and processes for making them | |
CA2386131A1 (en) | Detergent compositions | |
CA2386253A1 (en) | Washing methods utilizing an effervescent product added prior to agitation | |
CA2375497A1 (en) | Detergent particles and methods for making them | |
WO1999064558A1 (en) | Cleaning compositions containing speckle particles | |
CA2386948A1 (en) | Detergent compositions | |
GB2351500A (en) | Detergent compositions | |
EP1124929B1 (en) | Bleach-containing detergent composition | |
CA2365628A1 (en) | Detergent compositions | |
EP1159383A1 (en) | Detergent compositions | |
MXPA01005770A (en) | Effervescence components |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Discontinued |