WO2011061044A1 - Detergent granules - Google Patents
Detergent granules Download PDFInfo
- Publication number
- WO2011061044A1 WO2011061044A1 PCT/EP2010/066156 EP2010066156W WO2011061044A1 WO 2011061044 A1 WO2011061044 A1 WO 2011061044A1 EP 2010066156 W EP2010066156 W EP 2010066156W WO 2011061044 A1 WO2011061044 A1 WO 2011061044A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sodium carbonate
- las
- detergent
- surfactant
- habit modified
- Prior art date
Links
- 239000008187 granular material Substances 0.000 title claims abstract description 83
- 239000003599 detergent Substances 0.000 title claims abstract description 81
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 156
- 239000000203 mixture Substances 0.000 claims abstract description 89
- 239000004094 surface-active agent Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000002253 acid Substances 0.000 claims abstract description 53
- 230000008569 process Effects 0.000 claims abstract description 52
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 52
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 34
- 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 claims abstract description 33
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 33
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 33
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 16
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 16
- 239000010457 zeolite Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 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 claims abstract description 10
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
- 238000007046 ethoxylation reaction Methods 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000344 soap Substances 0.000 claims description 17
- 230000009471 action Effects 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000002304 perfume Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 53
- 235000017550 sodium carbonate Nutrition 0.000 description 50
- 239000000047 product Substances 0.000 description 34
- 239000003945 anionic surfactant Substances 0.000 description 22
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 19
- 239000011575 calcium Substances 0.000 description 17
- 239000007921 spray Substances 0.000 description 15
- -1 alkylbenzene sulphonate Chemical class 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 229920002125 Sokalan® Polymers 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 12
- 239000003607 modifier Substances 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229920005646 polycarboxylate Polymers 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 108010064470 polyaspartate Proteins 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 235000019832 sodium triphosphate Nutrition 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000005469 granulation Methods 0.000 description 5
- 239000008233 hard water Substances 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000008234 soft water Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 229920000805 Polyaspartic acid Polymers 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229960005261 aspartic acid Drugs 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 150000005323 carbonate salts Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000008202 granule composition Substances 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
- 238000005259 measurement Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 150000003385 sodium Chemical class 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- PTHBKNSHSCMKBV-UHFFFAOYSA-N 4,6,8-trihydroxy-3-(2-hydroxyethyl)-2,3-dihydronaphtho[2,3-f][1]benzofuran-5,10-dione Chemical compound O=C1C2=CC(O)=CC(O)=C2C(=O)C2=C1C=C1OCC(CCO)C1=C2O PTHBKNSHSCMKBV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002036 drum drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000014366 other mixer Nutrition 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011780 sodium chloride 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
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- PTHBKNSHSCMKBV-ZETCQYMHSA-N versicol Natural products OCC[C@H]1COc2cc3C(=O)c4cc(O)cc(O)c4C(=O)c3c(O)c12 PTHBKNSHSCMKBV-ZETCQYMHSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000004711 α-olefin 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
-
- 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
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- This invention relates to detergent granules comprising sodium carbonate and a mixed surfactant system including linear alkylbenzene sulphonate and nonionic surfactant.
- PCT/EP2009/054757 relates to a process for the manufacture of detergent granules comprising anionic non-soap surfactant, the process comprising the step of dry neutralisation of surfactant acid with habit modified Sodium Carbonate, which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer.
- compositions obtainable by the process in particular high active detergent granules
- anionic surfactant comprising a major part of non-soap anionic surfactant
- habit modified Sodium Carbonate which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer
- Granular laundry detergent compositions typically contain high levels of at least 10 wt% and usually more than 20 wt ⁇ 6 or even 30 wt% of zeolite and/or phosphate builder. These builders are not considered to be environmentally desirable for future laundry detergent compositions. The problem is to obtain new compositions which are stable and effective in the absence of these materials and which can be produced using equipment suitable for commercial scale operation. It is known that selection of certain surfactant blends gives rise to Calcium tolerance. In practice, this means that a composition with little or no builder will still provide satisfactory cleaning in the presence of hard water. Calcium tolerant formulations based on LAS (linear alkylbenzene
- the formulator will mix the LAS with a minor part of one or more co surfactants that significantly boost the ability of the surfactant system to give effective detergency in hard water without high levels of zeolite, phosphate, or even silicate builder in hard water.
- compositions include those using specific ratios of LAS to nonionic surfactant.
- the problem has been that to include significant total levels of surfactant in such
- compositions it has been found necessary to provide some form of carrier material, or to process the composition in a special way, to avoid lack of storage stability due to stickiness and caking and subsequent loss of flowability of the powder
- EP-A-420317 discloses a process for the continuous preparation of a granular detergent composition or component having a bulk density of at least 550 g/1, which comprises (i) feeding a liquid acid precursor of an anionic surfactant, a solid water- soluble alkaline inorganic material and optionally other materials into a high-speed mixer/densifier, the mean residence time being from about 5 to 30 seconds; (ii) subsequently treating the granular detergent material in a moderate-speed granulator/densifier, whereby it is brought into or maintained in a deformable state, the mean residence time being from about 1-10, preferably from 2-5 minutes; and finally (iii) drying and/or cooling the product.
- the solid water-soluble alkaline inorganic material may comprise sodium carbonate. This process is especially useful for producing compositions comprising alky
- the final high bulk density detergent product may for example comprise 5 to 60 wt percent of a builder, 5 to 25 wt percent carbonate, 5 to 40 wt percent anionic surfactant, 0 to 20 wt percent nonionic surfactant and 0 to 5 wt percent soap.
- EP-A-438 320 describes a batch process for the preparation of detergent powder of high bulk density.
- the process comprises neutralising a detergent acid (anionic surfactant precursor) , e.g. linear alkylbenzene sulphonic acid, with a particulate solid water-soluble alkaline inorganic material, for example Sodium Carbonate (optionally plus other alkaline materials and/or detergency builders, for example alkali metal
- aluminosilicate in a high-speed mixer/granulator, e.g. Fukae mixer, and granulating the product in the mixer.
- the reaction mixture remains particulate throughout the process, without the need to keep the temperature during the neutralisation step to 55°C or below, and a high-quality high-bulk-density particulate product is obtained.
- Nonionic surfactants that may be present include primary and secondary alcohol ethoxylates.
- the solids present during neutralisation may also include any other desired solid
- ingredients for example, fluorescers ; polycarboxylate
- compositions made all contain high levels of zeolite.
- GB-A-1 369 269 discloses a process for the neutralisation of synthetic organic anionic detergent acids, such as straight chain alkyl benzene sulphonic acid, by mixing the acid with an excess of powdered Sodium Carbonate in a modified mixer with a cutting arrangement, for example a Lodige ploughshare mixer.
- a builder and/or filler salt is taught to be added with the
- Examples 1 and 2 include Sodium
- Example 3 uses no Sodium Tripolyphosphate but the product requires pulverisation and is not described as free flowing. It is now desirable to exclude phosphate from
- GB-A-2 221 695 describes a dry neutralisation process for preparation of detergent powder of high bulk density in a high speed mixer granulator, with a stirring and a cutting action.
- zeolite or Sodium Tripolyphosphate is used in addition to Sodium Carbonate.
- very high levels of Sodium Carbonate are used and a special calcite flow aid is dosed at 4% to assist with the granulation.
- a special calcite flow aid is dosed at 4% to assist with the granulation.
- the flow properties of example 26 are very poor and addition of Sodium Tripolyphosphate is taught as a remedy for this problem.
- a problem with this process is that the use of a flow aid is a major process complication and it is now desirable to exclude phosphate from the granule.
- WO 2002/24854 describes a dry neutralisation process carried out in a horizontal thin-film evaporator drier. Use of small particle size Sodium Carbonate is taught to reduce the amount of unneutralised surfactant acid in the resulting product. Such unneutralised material is known to be undesirable as it
- zeolite is also added. This addition would reduce the level of anionic surfactant in the detergent granule. Furthermore, it is now desirable to be able to
- US-A-7 053 038 describes a dry neutralisation process carried out in a gas fluidisation granulator using small particle size Sodium Carbonate and an inorganic acid, such as sulphuric acid. Both zeolite and sodium tripolyphosphate are included in all the examples.
- EP-A-1 534 812 discloses dry neutralisation of preformed spray dried particles comprising a carbonate salt and polyacrylate .
- the process is carried out under low shear conditions in order to avoid agglomeration.
- the carbonate salt is the Burkeite double salt formed when Sodium Carbonate and sodium sulphate are spray dried together in a specified ratio. These particles are too strong to be used in the process of the present invention. As further explained later this process does not make habit modified Sodium Carbonate.
- EP-A-221 776 describes a process to spray dry Sodium Carbonate and a crystal growth modifier to make, so called, habit modified carbonate granules.
- the crystal growth modifier is preferably polymeric polycarboxylate .
- the patent describes the manufacture of habit modified Burkeite in the majority of the examples. Only example 1 crystal habit modifies Sodium
- habit modified Sodium Carbonate is a term used to encompass such prior art materials.
- the term does not include habit modified Burkeite, although low
- a detergent granule comprising:
- At least 20wt% habit modified Sodium Carbonate which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer
- SCMC Sodium carboxymethyl cellulose
- the detergent granule with the NI being an alkyl ethoxylate with a degree of ethoxylation of from 25EO to 35EO, preferably 30EO and the granule comprising (wt%) :
- the detergent granule can be made using a NI which is an alkyl ethoxylate with a degree of ethoxylation of from 5EO to 9EO and the granule comprises (wt %) :
- HMC 20 - 67 preferably 56 - 57
- the ratio of LAS:NI preferably lying in the range 80:20 to 70:30.
- the granules may further comprise perfume, soap, fluorescer,
- Granules that comprise less than 2wt% silicate are preferred, even more preferred are silicate free granules.
- a liquids: solids ratio of 0.3 to 0.4 produces excellent detergent granules, i.e. non-dusty, granular, and of acceptabl size and dissolution rate.
- Detergent granules having a total detergent active level from 25wt% to 45wt% with levels of habit modified sodium carbonate in excess of 20wt% may be produced stably for the first time by suitable adaptations of the process described in
- LAS/non-ionic 25-35EO preferably 30EO systems are effective at preventing surfactant loss by precipitation.
- the 30EO acts as a lime soap dispersant.
- the large wedge-shaped molecules disrupt the lamellae of CaLAS, and prevent precipitation.
- a 85/15 to 80/20 mix prevents precipitation across the entire range of water hardness, whereas a 90/10 blend will protect in soft water. If these surfactant systems produce insufficient lather for handwash, then other anionic surfactants, such as SLES, may be used in place of some or all of the highly ethoxylated
- 7EO non-ionic may also be used; it acts primarily by reducing the cmc of the surfactant blend, thereby reducing the level of LAS monomer. It is less weight-effective at preventing
- the 30EO nonionic is preferred over the 7EO nonionic.
- co-surfactants such as SLES and MES, also confer Ca tolerance when blended with LAS, but again, tend to be less weight-effective than high EO non-ionic.
- compositions are modified to take into account that a LAS/co-active ratio of between 80/20 and 70/30 is required to give Ca tolerance.
- the product may be formulated for use only in the handwash and TL machines. This means that a 85/15 ratio to confer Ca tolerance under all conditions is preferred. This will confer a lather level closer to that traditionally seen in the handwash:
- composition preferably comprises from 20 wt% to 70 wt% habit modified carbonate, more preferably 33 wt% to 70 wt%
- the habit modified carbonate is used in admixture with habit modified Burkeite and then the level of habit modified carbonate may be dropped to be at the lower end of the range of at least 20 wt%, preferably at least 30 wt%.
- Sodium Carbonate which comprises a mixture of Sodium Carbonate and polymer. Its manufacture is, for example, described in EP- A-221 776 and WO 2006/081930. It is not the same thing as habit modified Burkeite; the double salt of Sodium Carbonate and Sodium Sulphate.
- Habit modified Sodium Carbonate is further characterised by its specific surface area, measured by nitrogen adsorption.
- the specific surface area (“SSA”)of the Sodium Carbonate is
- the Habit modified Sodium Carbonate is characterised by having a specific surface area (SSA) of 5 m 2 /g or greater, preferably 8 m 2 /g or greater, even more preferably 10 m 2 /g or greater.
- SSA specific surface area
- the pore volume in pores less than 2 micron may further be provided.
- Over-granulation means that the discrete detergent granules begin to coalesce into a sticky mass and it is no longer possible to discharge them as a free flowing product without adding flow aid or other solid materials such as Zeolite or Sodium Tripolyphosphate . If the anionic Sodium Sulphonate surfactant level achieved is greater than 30 wt%, preferably greater than 35 wt%, more preferably greater than 45 wt%, then the Sodium Carbonate is habit modified for the purposes of this invention .
- Habit modified Sodium Carbonate herein also referred to as HMC
- HMC may be made by spray drying, as described in EP-A-221 776 and WO 2006/081930.
- Alternative drying methods as described in those patent applications, may also be employed: for example, air drying, oven drying, drum drying, ring drying, freeze drying, solvent drying, or microwave drying.
- HMC can also be made by precipitation of a saturated Sodium Carbonate solution, which further comprises a growth modifying polymer, in an evaporator, separating the precipitate; e.g. by filtration and drying the precipitate to habit modified Sodium Carbonate. The remaining solution is augmented with fresh
- Suitable crystal growth modifying polymers may be selected from polycarboxylates .
- Polyaspartates and polyaspartic acid are advantageously used due to their biodegradability .
- Preferred polymeric polycarboxylate crystal growth modifiers used in the invention are used in amounts of from 0.1 to 20 wt%, preferably from 0.2 to 5 wt%, most preferably 1 to 5 wt%, based on the total amount of Sodium Carbonate.
- higher levels of polymer for example, up to 60% by weight based on Sodium Carbonate, may be present in detergent granules of the invention, or full compositions comprising the detergent granules of the invention, for reasons other than crystal growth modification, for example, building, structuring or antiredeposition .
- the polycarboxylate crystal growth modifier preferably has a molecular weight of at least 1000, advantageously from 1000 to 300 000, especially from 1000 to 250 000. Polycarboxylate crystal growth modifiers having molecular weights in the 3000 to 100 000 range, especially 3500 to 70 000 and more especially 10 000 to 70 000 are preferred. All
- Preferred crystal growth modifiers are homopolymers and
- copolymers of acrylic acid or maleic acid are polyacrylates and acrylic acid/maleic acid copolymers.
- Suitable polymers which may be used alone or in combination, include the following: Salts of polyacrylic acid such as sodium polyacrylate, for example Versicol (Trade Mark) E5 E7 and E9 ex Allied Colloids, average molecular weights 3500, 27 000 and 70 000; Narlex (Trade Mark) LD 30 and 34 ex National Adhesives and Resins Ltd, average molecular weights 5000 and 25 000
- copolymers for example, the EMA (Trade Mark) series ex
- a second group of polymeric crystal growth modifiers comprises polyaspartic acids and polyaspartates .
- Preferred polymeric crystal growth modifiers in this second group have a molecular weight of at least 1000, advantageously from 3500 to 300000, especially from 4000 to 250000.
- HMC is preferably prepared using polyaspartate crystal growth
- modifiers having molecular weights in the 3500 to 100000 range, especially 4000 to 70000 and more especially 5000 to 70000. All molecular weights quoted herein are those provided by the manufacturers .
- Polyaspartate is a biopolymer synthesised from L-aspartic acid, a natural amino acid. Due in part to the carboxylate groups, polyaspartate has similar properties to polyacrylate .
- One preferred type of polyaspartate is thermal polyaspartate or TPA. This has the benefit of being biodegradable to
- TPA may be made by first heating aspartic acid to temperatures above 180 °C to produce polysuccinimide . Then the
- polysuccinimide is ring opened to form polyaspartate. Because the ring can open in two possible ways, two polymer linkages are observed, an [alpha] -linkage and a [beta] -linkage .
- Amounts of from 0.1 to 20 wt% of the crystal growth modifier, preferably from 0.2 to 5 wt%, most preferably 1 to 5 wt%, based on the total amount of Sodium Carbonate are generally
- the Sodium Carbonate used to make the habit modified Sodium Carbonate may be of any type. Synthetic light soda ash has been found to be especially preferred; natural heavy soda ash is intermediate, while synthetic granular soda ash is the least preferred raw material.
- the surfactant acid is an acid precursor of an anionic non-soap surfactant which, when reacted with habit modified Sodium
- Carbonate will be neutralised to form the sodium salt of the anionic surfactant.
- Surfactant acids in liquid, pumpable, form are preferred.
- a preferred class of anionic surfactants is alkyl aryl
- the preferred surfactant acid is linear alkyl benzene sulphonic acid, also referred to as LAS acid and HLAS .
- This surfactant acid gives a corresponding linear alkyl benzene sulphonate (LAS) upon neutralisation.
- the LAS non- soap anionic surfactant has an alkyl chain length of C8-18, more preferably ClO-16 and most preferably C12-14.
- surfactant acids include alpha-olefin sulphonic acids, internal olefin sulphonic acids, fatty acid ester sulphonic acids and primary sulphonic acids.
- Soaps formed by the dry neutralisation of carboxylic or fatty acids may be used as secondary anionic surfactants in admixture with the non-soap anionic surfactants.
- Preferred carboxylic acids are fatty acids with 12-18 carbon atoms, such as for example fatty acids of coconut oil, palm oil, palm kernel and tallow.
- the fatty acids may be saturated or unsaturated, branched or straight chain. Mixtures of fatty acids may be used.
- Fatty acids may be used at levels of up to 30 wt% based on the surfactant acid.
- the surfactant acid (or mixture of surfactant acids) may be used in a partially pre-neutralised form without loss of the advantageous effects of the invention. In effect, the
- surfactant acid is then a mixture of the surfactant acid with neutralised anionic non-soap surfactant.
- the detergent granules also comprise a conventional level of this polymer. Its inclusion adds strength to the granule during processing and it also confers benefits to the detergent composition .
- the HMC dry neutralisation process has all of the advantages and flexibility of prior art dry neutralisation processes.
- the surfactant acid may be added in admixture with other liquid components.
- other liquid components in addition to the fatty acids and neutralised anionic surfactant already discussed, the most important additional component that may be added as liquids with the surfactant acid is nonionic surfactant. This is typically added to the surfactant acid to reduce viscosity to enable it to be added at a lower temperature.
- Suitable nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8- C20 aliphatic alcohols ethoxylated with an average of from 1 to 50, preferably 1 to 20, moles ethylene oxide per mole of alcohol, and more especially the do-cis primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkyl-polyglycosides , glycerol monoethers, and polyhydroxyamides (glucamide) . As discussed already neutralised anionic surfactant may be mixed with the surfactant acid.
- Additional solid may be admixed with the habit modified Sodium Carbonate. This can be done either before or during
- Carbonate i.e. soda ash
- Zeolite and/or other builder materials could be added, although they are not needed to gain the good granule properties ascribed to the use of HMC . It is preferred to avoid use of zeolite completely, except perhaps as a final whitening coating.
- a complete detergent system can nevertheless be formulated into a single simple dry neutralised granule especially when Calcium tolerant surfactant blends are used. Calcium tolerant surfactant blends are those single or mixed surfactants, which do not require builders to be present for effective detergency across a normal range of water
- Calcium tolerant surfactant blends that may be dry neutralised include mixtures of LAS with nonionic high EO, SLES paste and/or AOS paste.
- alkalinity in the product an excess of about 10 to 15 wt% is then suitable. This represents a molar excess of 3:1 or more.
- the solids present in the mixer may also include other solid ingredients desired for inclusion in the detergent granule, for example, fluorescers ; polycarboxylate polymers;
- antiredeposition agents for example, sodium carboxymethyl cellulose; or fillers such as sodium sulphate, diatomaceous earth, calcite, kaolin or bentonite.
- fillers such as sodium sulphate, diatomaceous earth, calcite, kaolin or bentonite.
- solid particulate surfactants for example, alkylbenzene sulphonate and/or alkyl sulphate in powder form, may form part of the solids charge to the mixer to further increase the activity level of surfactant in the granule, however it is preferred to produce all the anionic surfactant by dry neutralisation.
- anionic surfactants that may be present in detergent granules prepared by the process of the invention include secondary alkyl sulphates, alkyl ether sulphates, and dialkyl sulphosuccinates .
- Anionic surfactants are of course well known and the skilled reader will be able to add to this list.
- neutralised paste surfactants are preferably added after the completion of neutralisation.
- the surfactant acid is preferably used in liquid form and advantageously it is reacted while mixing with a molar excess of habit modified Sodium Carbonate to form a sodium salt of the anionic surfactant, while mixing.
- a molar excess of habit modified Sodium Carbonate the reaction may be done with a mixture of habit modified Sodium Carbonate and a smaller amount of other conventional Sodium Carbonate, such as light ash and/or Burkeite, with a corresponding
- ingredients may be used in the dry neutralisation reaction. Because the system is self structuring, no zeolite or similar structurant is needed and the process is easy to control.
- the total amount of free water that can be tolerated in the process preferably should not amount to more than 8 wt% of the total composition, preferably not more than 4 wt%.
- the resulting granule will comprise neutralised anionic surfactant together with any excess habit modified Sodium Carbonate.
- the habit modified Sodium Carbonate is an excellent substrate for additional liquid components and it also functions in the same way as Sodium Carbonate as a buffer in a detergent composition.
- the invention may thus advantageously be used to prepare detergent powders in which Sodium Carbonate is used without any other builder present - especially if a Calcium tolerant surfactant blend or mixture is used. To ensure the presence of significant quantities of
- a process feature known to the person skilled in the art of dry neutralisation is that the surfactant acid should be added to the mixer sufficiently gradually so that it will be consumed immediately and will not accumulate in the mixer in unreacted form. We have found that this applies equally to the process using habit modified Sodium Carbonate.
- the time required and preferred for addition of the surfactant acid is of course dependent on the amount to be added, but in general addition preferably takes place over a period of at least 1 minute, more preferably over a period of from 2 to 12 minutes, most
- the process is generally not sensitive to the type of mixer used, provided intensive mixing is applied. We have found that to obtain the full advantages of the invention the use of a mixer with a chopping action is advantageous.
- the HMC starting material has a relatively low crush strength and the mixer should be selected so that it breaks up and rapidly provides fine, material with a consequent large total surface area for reaction and for regranulation . Thus, a conventional fluid bed granulator would not be preferred for the dry neutralisation process using habit modified carbonate.
- the mixing is carried out in a mixer having and using both a stirring action and a cutting action, most preferably these actions will be separately usable, as
- the cutting action is the preferred chopping action.
- This may be advantageously achieved by the choice of mixer to be a high-speed mixer/granulator having both a stirring action and a cutting action.
- the highspeed mixer/granulator has rotatable stirrer and cutter elements that can be operated independently of one another, and at separately changeable or variable speeds.
- Such a mixer is capable of combining a high-energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operation.
- the cutters would be off during the solids pre-mixing.
- a Lodige mixer is preferred, vertical or horizontal axis cutters are desirable for high anionic loading.
- mixers of the Fukae FS-G type manufactured by Fukae Powtech Co Ltd., Japan are also preferred; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
- the stirrer and cutter may be operated independently of one another, and at separately variable speeds.
- the vessel can be cooled .
- Yet another mixer found to be suitable for use in the process of the invention is the Lodige (Trade Mark) FM series batch mixer ex Morton Machine Co. Ltd., Scotland. This differs from the mixers mentioned above in that its stirrer has a horizontal axis.
- Z blade and sigma mixers are suitable mixers having a chopping action.
- the temperature of the powder mass in the mixer should be maintained throughout at 55°C or below, preferably below 50°C, more preferably below 47°C, and desirably below 40°C. If the temperature is allowed to rise too much, agglomeration and lump formation may occur.
- the granular product of the process is a particulate solid with a bulk density in the range 450 to 720 g/litre.
- the particle size distribution is generally such that at least 50 wt%, preferably at least 70 wt% and more preferably at least 85 wt%, of particles are smaller than 1700 microns, and the level of fines is low. No further treatment has generally been found to be necessary to remove either oversize particles or fines.
- the product has excellent flow properties, low compressibility and little tendency towards caking.
- the particulate detergent granules that are the direct result of the dry neutralisation process have a surfactant content of 25 wt% to 45 wt%.
- the absence of the need for a granulation aid such as zeolite, together with the ease that the reaction can be driven results in the potential to achieve high levels of surfactant in the granule without any processing difficulties or complications.
- the inclusion of nonionic surfactant often leads to stickiness but the high carrying capacity of the excess habit modified carbonate ensures that this is not thee case for the granules of the present invention.
- the fast reaction with the habit modified carbonate ensures that the granule becomes stable very quickly during the process and there is no concern about further neutralisation occurring which would require some sort of "aging" process.
- the detergent granules may also comprise water in an amount of 0 to 8% and preferably 0 to 4% by weight of the granules.
- the detergent granules obtained from the process are storage stable at high levels of humidity. Thus, they can be used in a wide range of detergent products.
- the detergent granules have an aspect ratio not in excess of two and more preferably are generally spherical in order to reduce segregation from other particles in a formulated powder detergent composition and to enhance the visual appearance of the powder.
- the detergent granules may be admixed with anything normally used in detergent formulations. They may be dry blended with solid materials and they may advantageously have further liquids added into them, using their spare liquid carrying capacity. It is especially advantageous to add conventional, or even higher than conventional, levels of perfume this way.
- non-soap surfactant for example, cationic, zwitterionic, amphoteric or semipolar surfactants, may also be used with the granules if desired.
- cationic, zwitterionic, amphoteric or semipolar surfactants may also be used with the granules if desired.
- suitable detergent- active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and
- Soap may also be present, to provide foam control and
- the fully formulated composition may comprise up to 8 wt% soap.
- Detergent compositions including the detergent granules prepared by the process of the invention may contain
- antiredeposition agents such as cellulosic polymers; anti incrustation agents, perfumes, dyes, shading dyes, fluorescers, sodium silicate; corrosion
- inhibitors including silicates; inorganic salts such as sodium sulphate, enzymes; coloured speckles; foam controllers; and fabric softening compounds.
- the detergent granule may if desired be mixed with other organic or inorganic builders, typically supplied in the form of granules of either pure builder or mixtures of builder and other ingredients.
- Especially preferred organic builders are acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10wt%. Such polymers may also fulfil the function of the habit modifying polymer .
- the skilled detergent formulator can decide which ingredients are suitable for admixture in the mixer, and which are not.
- the detergent granules may be mixed with another powder
- any conventional detergent production process including spray drying or non spray drying processes.
- such other powder is hereinafter called a base powder.
- the detergent granules produced by the present invention may be admixed with such other powders, a significant degree of formulation flexibility is obtained and the level of active material in the fully formulated composition may be very high without an unnecessary increase in builder levels.
- the total amount of surfactant present in the detergent composition is suitably from to 5 to 40 wt%, although amounts outside this range may be employed as desired.
- the detergent granules may typically constitute from 30 to 100 wt% of a final fully formulated detergent composition.
- the fully formulated detergent composition typically, the fully formulated detergent composition
- incorporating the detergent granules produced by the process of the invention may comprise from 5 to 45 wt%, preferably 10 to 35 wt% of anionic surfactant, this anionic surfactant being derived wholly or in part from the granular product of the dry neutralisation reaction.
- the process of the invention is of especial interest for the production of detergent powders or components containing relatively high levels of anionic
- the fully formulated detergent composition may comprise from 0 to 10 wt% of nonionic surfactant, and from 0 to 5 wt% of fatty acid soap.
- Fully formulated detergent compositions comprising other ingredients and the detergent granules produced by dry
- Powder flow may be quantified by means of the dynamic flow rate (DFR), in ml/s, measured by means of the following procedure.
- DFR dynamic flow rate
- the apparatus used consists of a cylindrical glass tube having an internal diameter of 35 mm and a length of 600 mm. The tube is securely clamped in a position such that its longitudinal axis is vertical. Its lower end is terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice of diameter 22.5 mm.
- a first beam sensor is positioned 150 mm above the outlet, and a second beam sensor is positioned 250 mm above the first sensor.
- the outlet orifice is temporarily closed, for example, by covering with a piece of card, and powder is poured through a funnel into the top of the cylinder until the powder level is about 10 cm higher than the upper sensor; a spacer between the funnel and the tube ensures that filling is uniform.
- the outlet is then opened and the time t (seconds) taken for the powder level to fall from the upper sensor to the lower sensor is measured electronically. The measurement is normally repeated two or three times and an average value taken. If V is the volume (ml) of the tube between the upper and lower sensors, the dynamic flow rate DFR (ml/s) is given by the following equation:
- the powder is loaded into a cylinder and the surface levelled.
- a 50 g plastic disc is placed on top of the powder and a 10 kg weighted plunger is placed slowly on top of the disc and allowed to remain in position for 2 minutes.
- the weight and plunger are then removed and the cylinder removed carefully from the powder to leave a free-standing cylinder of powder with the 50g plastic disc on top of it.
- a second 50 g plastic disc is placed on top of the first and left for approximately ten seconds.
- a 100 g disc is added to the plastic discs and left for ten seconds.
- the weight is then increased in 0.25 kg increments at 10 second intervals until the compact collapses.
- the total weight (w) needed to effect collapse is noted .
- the cohesiveness of a powder is classified by the weight (w) as follows : w ⁇ 1.0 kg Good flowing 1.0 kg ⁇ w ⁇ 2.0 kg Moderate flowing. 2.0 kg ⁇ w ⁇ 5.0 kg Cohesive. 5.0 kg ⁇ w Very cohesive.
- a 1-litre beaker is filled with 500mls of demineralised water at 20-25°C and stirred with a magnetic stirrer adjusted to give a vortex of about 4cm.
- a sample of powder is added to the water.
- the dissolution is measured according to solution conductivity.
- the T90' value is the time taken to achieve 90% of the final conductivity value.
- HMC was prepared according to WO 2006/081930 Al by mixing together 29.8 kg of Sokalan CP5 solution (40% active material) with 1373.8kg of water in a stirred tank. Into this solution was then dissolved 596.4 kg of light Sodium Carbonate (ex
- Mean size about 400 microns.
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Abstract
A detergent granule comprising: a) from 25 wt% to 45 wt% surfactant, comprising linear alkylbenzene sulphonic acid neutralised with habit modified carbonate to form sodium LAS and an ethoxylated nonionic surfactant having a degree of ethoxylation of from 5 to 50EO (NI), the granule having a LAS/NI ratio of from 90:10 to 70:30, preferably from 85:15 to 75:25, b) at least 20wt% habit modified Sodium Carbonate, which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer, and c) less than 10 wt%, preferably zero, zeolite, less than 1wt%, preferably zero phosphate, e) 0.2 wt% to 4 wt% Sodium carboxymethyl cellulose (SCMC) obtainable by a process comprising the dry neutralisation of liquid LAS acid with habit modified Sodium Carbonate, wherein the LAS acid is reacted while mixing with a molar excess of habit modified Sodium Carbonate to form Sodium LAS, while mixing.
Description
DETERGENT GRANULES
This invention relates to detergent granules comprising sodium carbonate and a mixed surfactant system including linear alkylbenzene sulphonate and nonionic surfactant.
BACKGROUND
PCT/EP2009/054757 relates to a process for the manufacture of detergent granules comprising anionic non-soap surfactant, the process comprising the step of dry neutralisation of surfactant acid with habit modified Sodium Carbonate, which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer.
That application also claims compositions obtainable by the process, in particular high active detergent granules
comprising :
a) greater than 30 wt% anionic surfactant, said surfactant comprising a major part of non-soap anionic surfactant, b) habit modified Sodium Carbonate, which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer, and
c) less than 10 wt%, preferably zero, zeolite.
Granular laundry detergent compositions typically contain high levels of at least 10 wt% and usually more than 20 wt~6 or even 30 wt% of zeolite and/or phosphate builder. These builders are not considered to be environmentally desirable for future laundry detergent compositions. The problem is to obtain new compositions which are stable and effective in the absence of these materials and which can be produced using equipment suitable for commercial scale operation.
It is known that selection of certain surfactant blends gives rise to Calcium tolerance. In practice, this means that a composition with little or no builder will still provide satisfactory cleaning in the presence of hard water. Calcium tolerant formulations based on LAS (linear alkylbenzene
sulphonate) are particularly favoured due to the easy
processability and commercial availability of that material. Typically, the formulator will mix the LAS with a minor part of one or more co surfactants that significantly boost the ability of the surfactant system to give effective detergency in hard water without high levels of zeolite, phosphate, or even silicate builder in hard water.
Such known compositions include those using specific ratios of LAS to nonionic surfactant. The problem has been that to include significant total levels of surfactant in such
compositions it has been found necessary to provide some form of carrier material, or to process the composition in a special way, to avoid lack of storage stability due to stickiness and caking and subsequent loss of flowability of the powder
composition .
In US4692275A a detergent composition is disclosed with an improved mixed surfactant system containing a C8-C18
alkylbenzene sulphonate and a C12-C18 alcohol ethoxysulphate formed with from 6 to 30 ethylene oxide units and having an average of 60-80% ethylene oxide by weight based on non- sulphated alcohol ethoxylate. The total amount of the
surfactants ranges from 10 to 20% and the ratio of sulphonate to sulphate is from 3.5:1 to 1.5:1. The compositions may further contain SCMC and fluorescent whitening agents.
EP-A-420317 discloses a process for the continuous preparation of a granular detergent composition or component having a bulk density of at least 550 g/1, which comprises (i) feeding a liquid acid precursor of an anionic surfactant, a solid water- soluble alkaline inorganic material and optionally other materials into a high-speed mixer/densifier, the mean residence time being from about 5 to 30 seconds; (ii) subsequently treating the granular detergent material in a moderate-speed granulator/densifier, whereby it is brought into or maintained in a deformable state, the mean residence time being from about 1-10, preferably from 2-5 minutes; and finally (iii) drying and/or cooling the product. The solid water-soluble alkaline inorganic material may comprise sodium carbonate. This process is especially useful for producing compositions comprising alkyl benzene sulphonates.
The final high bulk density detergent product may for example comprise 5 to 60 wt percent of a builder, 5 to 25 wt percent carbonate, 5 to 40 wt percent anionic surfactant, 0 to 20 wt percent nonionic surfactant and 0 to 5 wt percent soap.
EP-A-438 320 describes a batch process for the preparation of detergent powder of high bulk density. The process comprises neutralising a detergent acid (anionic surfactant precursor) , e.g. linear alkylbenzene sulphonic acid, with a particulate solid water-soluble alkaline inorganic material, for example Sodium Carbonate (optionally plus other alkaline materials and/or detergency builders, for example alkali metal
aluminosilicate) , in a high-speed mixer/granulator, e.g. Fukae mixer, and granulating the product in the mixer. The reaction mixture remains particulate throughout the process, without the need to keep the temperature during the neutralisation step to
55°C or below, and a high-quality high-bulk-density particulate product is obtained.
Nonionic surfactants that may be present include primary and secondary alcohol ethoxylates. The solids present during neutralisation may also include any other desired solid
ingredients, for example, fluorescers ; polycarboxylate
polymers; antiredeposition agents, for example, sodium
carboxymethyl cellulose; or fatty acids for in-situ
neutralisation to form soaps. The compositions made all contain high levels of zeolite.
GB-A-1 369 269 discloses a process for the neutralisation of synthetic organic anionic detergent acids, such as straight chain alkyl benzene sulphonic acid, by mixing the acid with an excess of powdered Sodium Carbonate in a modified mixer with a cutting arrangement, for example a Lodige ploughshare mixer. A builder and/or filler salt is taught to be added with the
Sodium Carbonate in order to make the product more free
flowing. The choppers or cutters in the mixer are used during addition of the acid. Examples 1 and 2 include Sodium
Tripolyphosphate in the dry mix. The powders produced are free flowing. Example 3 uses no Sodium Tripolyphosphate but the product requires pulverisation and is not described as free flowing. It is now desirable to exclude phosphate from
detergent granules, but this document does not teach an
effective process for its elimination.
GB-A-2 221 695 describes a dry neutralisation process for preparation of detergent powder of high bulk density in a high speed mixer granulator, with a stirring and a cutting action. In most of the examples, zeolite or Sodium Tripolyphosphate is used in addition to Sodium Carbonate. In examples 26 to 29,
very high levels of Sodium Carbonate are used and a special calcite flow aid is dosed at 4% to assist with the granulation. Despite this, the flow properties of example 26 are very poor and addition of Sodium Tripolyphosphate is taught as a remedy for this problem. A problem with this process is that the use of a flow aid is a major process complication and it is now desirable to exclude phosphate from the granule.
WO 2002/24854 describes a dry neutralisation process carried out in a horizontal thin-film evaporator drier. Use of small particle size Sodium Carbonate is taught to reduce the amount of unneutralised surfactant acid in the resulting product. Such unneutralised material is known to be undesirable as it
continues to react with the Sodium Carbonate and causes powder caking. In the examples, zeolite is also added. This addition would reduce the level of anionic surfactant in the detergent granule. Furthermore, it is now desirable to be able to
eliminate use of zeolite from a detergent granule if it is not essential in the formulation.
US-A-7 053 038 describes a dry neutralisation process carried out in a gas fluidisation granulator using small particle size Sodium Carbonate and an inorganic acid, such as sulphuric acid. Both zeolite and sodium tripolyphosphate are included in all the examples.
EP-A-1 534 812 discloses dry neutralisation of preformed spray dried particles comprising a carbonate salt and polyacrylate . The process is carried out under low shear conditions in order to avoid agglomeration. In all of the examples, the carbonate salt is the Burkeite double salt formed when Sodium Carbonate and sodium sulphate are spray dried together in a specified ratio. These particles are too strong to be used in the process
of the present invention. As further explained later this process does not make habit modified Sodium Carbonate.
EP-A-221 776 describes a process to spray dry Sodium Carbonate and a crystal growth modifier to make, so called, habit modified carbonate granules. The crystal growth modifier is preferably polymeric polycarboxylate . The patent describes the manufacture of habit modified Burkeite in the majority of the examples. Only example 1 crystal habit modifies Sodium
Carbonate itself.
Habit modified Sodium Carbonate is also spray dried for use as a carrier granule in WO 2006/081930. Polyaspartates are used in place of the polycarboxylates of EP-A-221 776.
Throughout this specification habit modified Sodium Carbonate is a term used to encompass such prior art materials. The term does not include habit modified Burkeite, although low
concentrations of Burkeite could conceivably be included in admixture with the desired habit modified Sodium Carbonate provided that the resulting admixture remains characterised as described below.
It is an object of the present invention to provide detergent granules comprising habit modified Sodium Carbonate and novel surfactant mixtures, which exhibit improved storage and
handling properties.
SUMMARY OF THE INVENTION
According to the present invention, there is provided a detergent granule comprising:
a) from 25 wt% to 45 wt% surfactant, comprising linear
alkylbenzene sulphonic acid neutralised with habit modified
carbonate to form sodium LAS and an ethoxylated nonionic surfactant having a degree of ethoxylation of from 5 to 50EO (NI), the granule having a LAS/NI ratio of from 90:10 to 70:30, preferably from 85:15 to 75:25,
b) at least 20wt% habit modified Sodium Carbonate, which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer, and
c) less than 10 wt%, preferably zero, zeolite, less than lwt%, preferably zero phosphate, e) 0.2 wt% to 4 wt% Sodium carboxymethyl cellulose (SCMC) obtainable by a process comprising the dry neutralisation of liquid LAS acid with habit modified Sodium Carbonate, wherein the LAS acid is reacted while mixing with a molar excess of habit modified Sodium Carbonate to form Sodium LAS, while mixing .
To achieve a calcium tolerant surfactant system that will work extremely effectively over a wide ranges of wash conditions and water hardness it is preferred to formulate the detergent granule with the NI being an alkyl ethoxylate with a degree of ethoxylation of from 25EO to 35EO, preferably 30EO and the granule comprising (wt%) :
LAS 25 - 34
NI 25-35EO 2.9 - 7.5
Habit Modified Carbonate 20-67, preferably 56 - 67
SCMC 0.2 - 4
Water and minors balance
Alternatively it is possible to use a more conventional
nonionic but with some reduction in the tolerance towards higher calcium and magnesium levels. In this case the detergent
granule can be made using a NI which is an alkyl ethoxylate with a degree of ethoxylation of from 5EO to 9EO and the granule comprises (wt %) :
LAS 22 - 30
NI 5-9EO 5.5 - 11.5
HMC 20 - 67, preferably 56 - 57
SCMC 0.2 - 4
Water and balance
The ratio of LAS:NI preferably lying in the range 80:20 to 70:30.
The granules may further comprise perfume, soap, fluorescer,
Granules that comprise less than 2wt% silicate are preferred, even more preferred are silicate free granules.
A liquids: solids ratio of 0.3 to 0.4 produces excellent detergent granules, i.e. non-dusty, granular, and of acceptabl size and dissolution rate.
Detergent granules having a total detergent active level from 25wt% to 45wt% with levels of habit modified sodium carbonate in excess of 20wt% may be produced stably for the first time by suitable adaptations of the process described in
PCT/EP2009/054757 and explained in detail in the following description . For soft water, a LAS/NI 30EO ratio of 90/10 will confer Ca tolerance. Medium to hard water requires a ratio in the range 85/15 to 80/20.
The granules may be used with a minor amount of separate granules comprising antifoam, enzyme, cleaning polymers as described in more detail below. Choice of Co-Surfactant (for LAS)
LAS/non-ionic 25-35EO, preferably 30EO systems are effective at preventing surfactant loss by precipitation. The 30EO acts as a lime soap dispersant. The large wedge-shaped molecules disrupt the lamellae of CaLAS, and prevent precipitation. A 85/15 to 80/20 mix prevents precipitation across the entire range of water hardness, whereas a 90/10 blend will protect in soft water. If these surfactant systems produce insufficient lather for handwash, then other anionic surfactants, such as SLES, may be used in place of some or all of the highly ethoxylated
(30EO) non-ionic.
7EO non-ionic may also be used; it acts primarily by reducing the cmc of the surfactant blend, thereby reducing the level of LAS monomer. It is less weight-effective at preventing
precipitation than the 30EO, and an 80/20 to 70/30 LAS/non- ionic blend is required to offer full Ca-tolerance. Therefore, the 30EO nonionic is preferred over the 7EO nonionic.
Other co-surfactants, such as SLES and MES, also confer Ca tolerance when blended with LAS, but again, tend to be less weight-effective than high EO non-ionic.
Advantageously granules for use in formulations with a LAS/non- ionic 30EO system containing < 85% LAS are used to give good cleaning across all water hardness.
For use of non-ionic 7EO, SLES or MES surfactant in place of the 30EO non-ionic, the compositions are modified to take into
account that a LAS/co-active ratio of between 80/20 and 70/30 is required to give Ca tolerance.
In this case, those formulations in which the LAS/NI 7EO system contains < 80% LAS deliver adequate cleaning across all water hardness .
In many regions, Front loading automatic (FLA) machines are used. To have a common formulation chassis across handwash, top-loaders and front-loaders, it is preferable to operate wi an 80/20 LAS/NI ratio to minimise the need for antifoam. In that case, the preferred 30EO granule compositions become:
LAS 23 - 30
NI 30 EO 5.7 - 7
HM Carbonate 56 - 67
SCMC 0.2 - 4
Water and minors balance In other areas, FLA machines are either non-existent, or of minimal importance. In that case, the product may be formulated for use only in the handwash and TL machines. This means that a 85/15 ratio to confer Ca tolerance under all conditions is preferred. This will confer a lather level closer to that traditionally seen in the handwash:
LAS 24 - 32
NI 30 EO 4.3 - 5.7
Carbonate 56 - 67
SCMC 0.2 - 4
Water & minors 0.5 - 0.7
For soft water, a LAS/NI 30EO ratio of 90/10 will confer Ca tolerance. Medium to hard water requires a ratio in the range 85/15 to 80/20. For optimum cleaning, lack of stickiness and processability the level of detergent active is advantageously greater than 27.5 wt% even more advantageously greater than 30 wt%. The
composition preferably comprises from 20 wt% to 70 wt% habit modified carbonate, more preferably 33 wt% to 70 wt%
However, in one embodiment of the invention the habit modified carbonate is used in admixture with habit modified Burkeite and then the level of habit modified carbonate may be dropped to be at the lower end of the range of at least 20 wt%, preferably at least 30 wt%.
DETAILED DESCRIPTION OF THE INVENTION
The habit modified Sodium Carbonate (HMC)
Habit modified Sodium Carbonate is a crystal growth modified
Sodium Carbonate, which comprises a mixture of Sodium Carbonate and polymer. Its manufacture is, for example, described in EP- A-221 776 and WO 2006/081930. It is not the same thing as habit modified Burkeite; the double salt of Sodium Carbonate and Sodium Sulphate.
It is essential that the polymer used as crystal growth
modifier is present when crystallisation of the habit modified Sodium Carbonate occurs, that is to say, it must be
incorporated not later than the Sodium Carbonate.
Habit modified Sodium Carbonate is further characterised by its specific surface area, measured by nitrogen adsorption. The
specific surface area ("SSA")of the Sodium Carbonate is
measured by nitrogen absorption according to ASTM D 3663-78 standard based upon the Brunauer, Emmett, and Teller (BET) method described in J. Am. Chem. Soc. 60, 309 (1938) . We used a Gemini Model 2360 surface area analyzer (available from
Micromeritics Instrument Corp. of Norcross, Ga . ) .
The Habit modified Sodium Carbonate is characterised by having a specific surface area (SSA) of 5 m2/g or greater, preferably 8 m2/g or greater, even more preferably 10 m2/g or greater.
The pore volume in pores less than 2 micron may further
characterise the habit modified Sodium carbonate. This is measured by a conventional mercury porosimetry method. Pore volumes of 0.3 ml/g or greater are advantageous.
An alternative characterisation of the habit modified Sodium Carbonate, comprising polymer and Sodium Carbonate, is to use it in the process of claim 1 with sulphonic acid and to
determine the maximum Sodium Sulphonate anionic non-soap surfactant levels achievable before over-granulation occurs. Over-granulation means that the discrete detergent granules begin to coalesce into a sticky mass and it is no longer possible to discharge them as a free flowing product without adding flow aid or other solid materials such as Zeolite or Sodium Tripolyphosphate . If the anionic Sodium Sulphonate surfactant level achieved is greater than 30 wt%, preferably greater than 35 wt%, more preferably greater than 45 wt%, then the Sodium Carbonate is habit modified for the purposes of this invention .
Habit modified Sodium Carbonate, herein also referred to as HMC, may be made by spray drying, as described in EP-A-221 776 and WO 2006/081930. Alternative drying methods, as described in
those patent applications, may also be employed: for example, air drying, oven drying, drum drying, ring drying, freeze drying, solvent drying, or microwave drying. HMC can also be made by precipitation of a saturated Sodium Carbonate solution, which further comprises a growth modifying polymer, in an evaporator, separating the precipitate; e.g. by filtration and drying the precipitate to habit modified Sodium Carbonate. The remaining solution is augmented with fresh
Sodium Carbonate solution and polymer solution and returned to the evaporator. The advantage of a precipitation process over one that relies entirely on drying is that energy consumption is lower. The polymer
An essential component of habit modified Sodium Carbonate is the polymer. Suitable crystal growth modifying polymers may be selected from polycarboxylates . Polyaspartates and polyaspartic acid are advantageously used due to their biodegradability .
Preferred polymeric polycarboxylate crystal growth modifiers used in the invention are used in amounts of from 0.1 to 20 wt%, preferably from 0.2 to 5 wt%, most preferably 1 to 5 wt%, based on the total amount of Sodium Carbonate. However, higher levels of polymer, for example, up to 60% by weight based on Sodium Carbonate, may be present in detergent granules of the invention, or full compositions comprising the detergent granules of the invention, for reasons other than crystal growth modification, for example, building, structuring or antiredeposition .
The polycarboxylate crystal growth modifier preferably has a molecular weight of at least 1000, advantageously from 1000 to 300 000, especially from 1000 to 250 000. Polycarboxylate crystal growth modifiers having molecular weights in the 3000 to 100 000 range, especially 3500 to 70 000 and more especially 10 000 to 70 000 are preferred. All
molecular weights quoted herein are those provided by the manufacturers .
Preferred crystal growth modifiers are homopolymers and
copolymers of acrylic acid or maleic acid. Of especial interest are polyacrylates and acrylic acid/maleic acid copolymers. Suitable polymers, which may be used alone or in combination, include the following: Salts of polyacrylic acid such as sodium polyacrylate, for example Versicol (Trade Mark) E5 E7 and E9 ex Allied Colloids, average molecular weights 3500, 27 000 and 70 000; Narlex (Trade Mark) LD 30 and 34 ex National Adhesives and Resins Ltd, average molecular weights 5000 and 25 000
respectively; and Sokalan (Trade Mark) PA range ex BASF, average molecular weight 250 000; ethylene/maleic acid
copolymers, for example, the EMA (Trade Mark) series ex
Monsanto; methyl vinyl ether/maleic acid copolymers, for example Gantrez (Trade Mark) AN119 ex GAF Corporation; acrylic acid/maleic acid copolymers, for example, Sokalan (Trade Mark) CP5 ex BASF.
A second group of polymeric crystal growth modifiers comprises polyaspartic acids and polyaspartates .
Preferred polymeric crystal growth modifiers in this second group have a molecular weight of at least 1000, advantageously
from 3500 to 300000, especially from 4000 to 250000. HMC is preferably prepared using polyaspartate crystal growth
modifiers having molecular weights in the 3500 to 100000 range, especially 4000 to 70000 and more especially 5000 to 70000. All molecular weights quoted herein are those provided by the manufacturers .
Polyaspartate is a biopolymer synthesised from L-aspartic acid, a natural amino acid. Due in part to the carboxylate groups, polyaspartate has similar properties to polyacrylate . One preferred type of polyaspartate is thermal polyaspartate or TPA. This has the benefit of being biodegradable to
environmentally benign products, such as carbon dioxide and water, which avoids the need for removal of TPA during sewage treatment, and its disposal to landfill.
TPA may be made by first heating aspartic acid to temperatures above 180 °C to produce polysuccinimide . Then the
polysuccinimide is ring opened to form polyaspartate. Because the ring can open in two possible ways, two polymer linkages are observed, an [alpha] -linkage and a [beta] -linkage .
Amounts of from 0.1 to 20 wt% of the crystal growth modifier, preferably from 0.2 to 5 wt%, most preferably 1 to 5 wt%, based on the total amount of Sodium Carbonate are generally
sufficient to produce suitable habit modified Sodium Carbonate.
Mixtures of any two or more polymeric crystal growth modifiers may, if desired, be used in the process and detergent granule compositions of the invention.
The Sodium Carbonate
The Sodium Carbonate used to make the habit modified Sodium Carbonate may be of any type. Synthetic light soda ash has been found to be especially preferred; natural heavy soda ash is intermediate, while synthetic granular soda ash is the least preferred raw material.
Mixed habit modified carbonate and habit modified Burkeite
By using a mixture of Sodium carbonate and Sodium sulphate in the starting material, it is possible to incorporate some
Sodium Sulphate into the final product. We have found that it is essential to habit modify the Sodium sulphate to make habit modified Burkeite in admixture with the habit modified
Carbonate. Any attempt to add significant quantities of non habit modified Sodium sulphate at any subsequent point in the process results in a granule with insufficient carrying
capacity and caking will occur for the levels of Calcium tolerant actives needed. It is important to distinguish the present invention from the prior art use of Burkeite. In the prior art the ratio of Carbonate to Sulphate was adjusted to ensure that nearly all of the habit modified material would be habit modified Burkeite. In contrast to this, we adjust the ratio to ensure that at least 20 wt% habit modified carbonate is always present in the detergent granule. This habit modified carbonate material confers the required properties to the granule. The Sodium Carbonate can be identified as a separate component from any Burkeite by XRD, for example.
The surfactant acid
The surfactant acid is an acid precursor of an anionic non-soap surfactant which, when reacted with habit modified Sodium
Carbonate will be neutralised to form the sodium salt of the
anionic surfactant. Surfactant acids in liquid, pumpable, form are preferred.
A preferred class of anionic surfactants is alkyl aryl
sulphonates. The preferred surfactant acid is linear alkyl benzene sulphonic acid, also referred to as LAS acid and HLAS . This surfactant acid gives a corresponding linear alkyl benzene sulphonate (LAS) upon neutralisation. Preferably, the LAS non- soap anionic surfactant has an alkyl chain length of C8-18, more preferably ClO-16 and most preferably C12-14.
Other suitable surfactant acids include alpha-olefin sulphonic acids, internal olefin sulphonic acids, fatty acid ester sulphonic acids and primary sulphonic acids.
It is also possible to use combinations of surfactant acids as will be apparent to the skilled person.
Soaps formed by the dry neutralisation of carboxylic or fatty acids may be used as secondary anionic surfactants in admixture with the non-soap anionic surfactants. Preferred carboxylic acids are fatty acids with 12-18 carbon atoms, such as for example fatty acids of coconut oil, palm oil, palm kernel and tallow. The fatty acids may be saturated or unsaturated, branched or straight chain. Mixtures of fatty acids may be used. Fatty acids may be used at levels of up to 30 wt% based on the surfactant acid.
The surfactant acid (or mixture of surfactant acids) may be used in a partially pre-neutralised form without loss of the advantageous effects of the invention. In effect, the
surfactant acid is then a mixture of the surfactant acid with neutralised anionic non-soap surfactant.
Sodium carboxymethyl cellulose
The detergent granules also comprise a conventional level of this polymer. Its inclusion adds strength to the granule during processing and it also confers benefits to the detergent composition .
Optional further ingredients present during the process
The HMC dry neutralisation process has all of the advantages and flexibility of prior art dry neutralisation processes.
The surfactant acid may be added in admixture with other liquid components. Among these, in addition to the fatty acids and neutralised anionic surfactant already discussed, the most important additional component that may be added as liquids with the surfactant acid is nonionic surfactant. This is typically added to the surfactant acid to reduce viscosity to enable it to be added at a lower temperature. Suitable nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8- C20 aliphatic alcohols ethoxylated with an average of from 1 to 50, preferably 1 to 20, moles ethylene oxide per mole of alcohol, and more especially the do-cis primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl-polyglycosides , glycerol monoethers, and polyhydroxyamides (glucamide) . As discussed already neutralised anionic surfactant may be mixed with the surfactant acid. This can have the advantage of increasing throughput of the reaction vessel/mixer.
Use of specific mixtures of LAS and Nonionic surfactant gives a good calcium tolerance to the compositions, particularly when the blend is used at medium active levels as defined above. Two particularly preferred nonionic are 30EO and 7EO materials. The 30EO material gives calcium tolerance at longer ratios of LAS to Nonionic. This is described in more detail under the description of the resulting granule below. Other liquid additives that may be added with the anionic surfactant acid, or added as separate liquid stream (s) , include inorganic acids, such as sulphuric acid, and hydrotropes, such as para toluene sulphonic acid. A small amount of water, sufficient to initiate the
neutralisation reaction but not sufficient to cause substantial agglomeration, may be premixed with the surfactant acid before the latter is introduced into the mixer, but addition of water is not essential. If a coloured product is desired, dyestuff may conveniently be premixed with the surfactant acid and water before addition to the mixer. The amount of water to be added may up to about 2 wt% based on the total granule ingredients.
Additional solid may be admixed with the habit modified Sodium Carbonate. This can be done either before or during
neutralisation of the surfactant acid. Unmodified Sodium
Carbonate, i.e. soda ash, may be used in admixture with the habit modified Sodium Carbonate. Zeolite and/or other builder materials could be added, although they are not needed to gain the good granule properties ascribed to the use of HMC . It is preferred to avoid use of zeolite completely, except perhaps as a final whitening coating. A complete detergent system can nevertheless be formulated into a single simple dry neutralised
granule especially when Calcium tolerant surfactant blends are used. Calcium tolerant surfactant blends are those single or mixed surfactants, which do not require builders to be present for effective detergency across a normal range of water
hardness. We use the following method to test a surfactant blend for Calcium-tolerance. First 0.7 g/L of the surfactant blend are dissolved in water containing sufficient Calcium ions to give a French hardness of 40 (4 x 10~3 Molar Ca2+) . Other electrolytes such as Sodium Chloride, Sodium Sulphate, and Sodium hydroxide are then added as necessary to adjust the ionic strength to 0.05M and the pH to 10. The adsorption of light of wavelength 540 nm through 4 mm of sample is measured 15 minutes after sample preparation. Ten measurements are made and an average value is calculated. Calcium tolerant blends are those that give an average value of less than 0.08.
Calcium tolerant surfactant blends that may be dry neutralised include mixtures of LAS with nonionic high EO, SLES paste and/or AOS paste.
In addition to the essential habit modified Sodium Carbonate, conventional builders and non habit modified Sodium Carbonate may also be added to the mixer. Examples of such builders include crystalline and amorphous alkali metal
aluminosilicates , alkali metal phosphates, and mixtures
thereof. The total of habit modified Sodium Carbonate and
Sodium Carbonate should always be present in excess of the amount required for neutralisation, in order to provide
alkalinity in the product: an excess of about 10 to 15 wt% is then suitable. This represents a molar excess of 3:1 or more.
The solids present in the mixer may also include other solid ingredients desired for inclusion in the detergent granule, for
example, fluorescers ; polycarboxylate polymers;
antiredeposition agents, for example, sodium carboxymethyl cellulose; or fillers such as sodium sulphate, diatomaceous earth, calcite, kaolin or bentonite. However, as discussed above we have found that if sodium sulphate is used it also should be habit modified.
If desired, solid particulate surfactants, for example, alkylbenzene sulphonate and/or alkyl sulphate in powder form, may form part of the solids charge to the mixer to further increase the activity level of surfactant in the granule, however it is preferred to produce all the anionic surfactant by dry neutralisation. Other anionic surfactants that may be present in detergent granules prepared by the process of the invention include secondary alkyl sulphates, alkyl ether sulphates, and dialkyl sulphosuccinates . Anionic surfactants are of course well known and the skilled reader will be able to add to this list.
However, neutralised paste surfactants are preferably added after the completion of neutralisation.
The dry neutralisation process
The surfactant acid is preferably used in liquid form and advantageously it is reacted while mixing with a molar excess of habit modified Sodium Carbonate to form a sodium salt of the anionic surfactant, while mixing. As an alternative to use of a molar excess of habit modified Sodium Carbonate the reaction may be done with a mixture of habit modified Sodium Carbonate and a smaller amount of other conventional Sodium Carbonate, such as light ash and/or Burkeite, with a corresponding
reduction in the granulation benefits of the invention.
Nevertheless, if large amounts of Sodium Carbonate are to be
used this hybrid process reduces the amount of specially habit modified raw material needed.
A wider than normal range of ratios of liquid to solid
ingredients may be used in the dry neutralisation reaction. Because the system is self structuring, no zeolite or similar structurant is needed and the process is easy to control.
The total amount of free water that can be tolerated in the process preferably should not amount to more than 8 wt% of the total composition, preferably not more than 4 wt%.
When habit modified Sodium Carbonate is used in the dry
neutralisation process then the resulting granule will comprise neutralised anionic surfactant together with any excess habit modified Sodium Carbonate. The habit modified Sodium Carbonate is an excellent substrate for additional liquid components and it also functions in the same way as Sodium Carbonate as a buffer in a detergent composition. The invention may thus advantageously be used to prepare detergent powders in which Sodium Carbonate is used without any other builder present - especially if a Calcium tolerant surfactant blend or mixture is used. To ensure the presence of significant quantities of
Sodium Carbonate in the granule substantially more habit modified Sodium Carbonate than is required for neutralisation may be present.
A process feature known to the person skilled in the art of dry neutralisation is that the surfactant acid should be added to the mixer sufficiently gradually so that it will be consumed immediately and will not accumulate in the mixer in unreacted form. We have found that this applies equally to the process using habit modified Sodium Carbonate. The time required and
preferred for addition of the surfactant acid is of course dependent on the amount to be added, but in general addition preferably takes place over a period of at least 1 minute, more preferably over a period of from 2 to 12 minutes, most
preferably from 3 to 10 minutes.
The mixer
The process is generally not sensitive to the type of mixer used, provided intensive mixing is applied. We have found that to obtain the full advantages of the invention the use of a mixer with a chopping action is advantageous. The HMC starting material has a relatively low crush strength and the mixer should be selected so that it breaks up and rapidly provides fine, material with a consequent large total surface area for reaction and for regranulation . Thus, a conventional fluid bed granulator would not be preferred for the dry neutralisation process using habit modified carbonate.
Preferably, the mixing is carried out in a mixer having and using both a stirring action and a cutting action, most preferably these actions will be separately usable, as
described below. The cutting action is the preferred chopping action. This may be advantageously achieved by the choice of mixer to be a high-speed mixer/granulator having both a stirring action and a cutting action. Preferably, the highspeed mixer/granulator has rotatable stirrer and cutter elements that can be operated independently of one another, and at separately changeable or variable speeds. Such a mixer is capable of combining a high-energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operation. The cutters would be off during the solids pre-mixing.
A Lodige mixer is preferred, vertical or horizontal axis cutters are desirable for high anionic loading. Also preferred are mixers of the Fukae FS-G type manufactured by Fukae Powtech Co Ltd., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
The stirrer and cutter may be operated independently of one another, and at separately variable speeds. The vessel can be cooled .
Other mixers believed to be suitable for use in the process of the invention are the Fuji (Trade Mark) VG-C series ex Fuji Sangyo Co., Japan; and the Roto (Trade Mark) ex Zanchetta & Co srl, Italy.
Yet another mixer found to be suitable for use in the process of the invention is the Lodige (Trade Mark) FM series batch mixer ex Morton Machine Co. Ltd., Scotland. This differs from the mixers mentioned above in that its stirrer has a horizontal axis. Z blade and sigma mixers (Winkworth machinery limited) are suitable mixers having a chopping action. The temperature of the powder mass in the mixer should be maintained throughout at 55°C or below, preferably below 50°C, more preferably below 47°C, and desirably below 40°C. If the temperature is allowed to rise too much, agglomeration and lump formation may occur.
The detergent granule
The granular product of the process is a particulate solid with a bulk density in the range 450 to 720 g/litre. The particle
size distribution is generally such that at least 50 wt%, preferably at least 70 wt% and more preferably at least 85 wt%, of particles are smaller than 1700 microns, and the level of fines is low. No further treatment has generally been found to be necessary to remove either oversize particles or fines.
The product has excellent flow properties, low compressibility and little tendency towards caking. The particulate detergent granules that are the direct result of the dry neutralisation process have a surfactant content of 25 wt% to 45 wt%. The absence of the need for a granulation aid such as zeolite, together with the ease that the reaction can be driven results in the potential to achieve high levels of surfactant in the granule without any processing difficulties or complications. The inclusion of nonionic surfactant often leads to stickiness but the high carrying capacity of the excess habit modified carbonate ensures that this is not thee case for the granules of the present invention. Furthermore the fast reaction with the habit modified carbonate ensures that the granule becomes stable very quickly during the process and there is no concern about further neutralisation occurring which would require some sort of "aging" process.
The detergent granules may also comprise water in an amount of 0 to 8% and preferably 0 to 4% by weight of the granules.
The detergent granules obtained from the process are storage stable at high levels of humidity. Thus, they can be used in a wide range of detergent products.
Desirably the detergent granules have an aspect ratio not in excess of two and more preferably are generally spherical in order to reduce segregation from other particles in a
formulated powder detergent composition and to enhance the visual appearance of the powder.
Further processing
If desired, further ingredients may be admixed to the detergent granules after they have been manufactured.
The detergent granules may be admixed with anything normally used in detergent formulations. They may be dry blended with solid materials and they may advantageously have further liquids added into them, using their spare liquid carrying capacity. It is especially advantageous to add conventional, or even higher than conventional, levels of perfume this way.
Other types of non-soap surfactant, for example, cationic, zwitterionic, amphoteric or semipolar surfactants, may also be used with the granules if desired. Many suitable detergent- active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and
Detergents", Volumes I and II, by Schwartz, Perry and Berch.
Soap may also be present, to provide foam control and
additional detergency and builder power. The fully formulated composition may comprise up to 8 wt% soap. Detergent compositions including the detergent granules prepared by the process of the invention may contain
conventional amounts of other detergent ingredients, for example, bleaches, enzymes, lather boosters or lather
controllers as appropriate, antiredeposition agents such as cellulosic polymers; anti incrustation agents, perfumes, dyes, shading dyes, fluorescers, sodium silicate; corrosion
inhibitors including silicates; inorganic salts such as sodium sulphate, enzymes; coloured speckles; foam controllers; and
fabric softening compounds. The detergent granule may if desired be mixed with other organic or inorganic builders, typically supplied in the form of granules of either pure builder or mixtures of builder and other ingredients.
Especially preferred organic builders are acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10wt%. Such polymers may also fulfil the function of the habit modifying polymer .
The skilled detergent formulator can decide which ingredients are suitable for admixture in the mixer, and which are not.
The detergent granules may be mixed with another powder
obtained from any conventional detergent production process including spray drying or non spray drying processes. For convenience, such other powder is hereinafter called a base powder. As the detergent granules produced by the present invention may be admixed with such other powders, a significant degree of formulation flexibility is obtained and the level of active material in the fully formulated composition may be very high without an unnecessary increase in builder levels. The total amount of surfactant present in the detergent composition is suitably from to 5 to 40 wt%, although amounts outside this range may be employed as desired.
The detergent granules may typically constitute from 30 to 100 wt% of a final fully formulated detergent composition.
Typically, the fully formulated detergent composition
incorporating the detergent granules produced by the process of the invention may comprise from 5 to 45 wt%, preferably 10 to 35 wt% of anionic surfactant, this anionic surfactant being derived wholly or in part from the granular product of the dry
neutralisation reaction. The process of the invention is of especial interest for the production of detergent powders or components containing relatively high levels of anionic
surfactant, for example, 15 to 30 wt%, more especially 20 to 30 wt%. In addition, the fully formulated detergent composition may comprise from 0 to 10 wt% of nonionic surfactant, and from 0 to 5 wt% of fatty acid soap.
Fully formulated detergent compositions, comprising other ingredients and the detergent granules produced by dry
neutralisation of habit modified Sodium Carbonate; preferably have a bulk density of at least 400 g/1, more preferably at least 450 g/litre. The invention will now be further described with reference to the following non limiting examples. In the examples, in addition to the SSA, pore volume and loading tests described above, the detergent granule properties are measured according to the following known test protocols.
Dynamic flow rate (DFR)
This is also called flow-rate. Powder flow may be quantified by means of the dynamic flow rate (DFR), in ml/s, measured by means of the following procedure. The apparatus used consists of a cylindrical glass tube having an internal diameter of 35 mm and a length of 600 mm. The tube is securely clamped in a position such that its longitudinal axis is vertical. Its lower end is terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice of diameter 22.5 mm. A first beam sensor is positioned 150 mm above the outlet, and a second beam sensor is positioned 250 mm above the first sensor.
To determine the dynamic flow rate of a powder sample, the outlet orifice is temporarily closed, for example, by covering with a piece of card, and powder is poured through a funnel into the top of the cylinder until the powder level is about 10 cm higher than the upper sensor; a spacer between the funnel and the tube ensures that filling is uniform. The outlet is then opened and the time t (seconds) taken for the powder level to fall from the upper sensor to the lower sensor is measured electronically. The measurement is normally repeated two or three times and an average value taken. If V is the volume (ml) of the tube between the upper and lower sensors, the dynamic flow rate DFR (ml/s) is given by the following equation:
DFR = V ml/s
t
Unconfined Compression Test (UCT)
In this test, freshly produced powder is compressed into a compact and the force required to break the compact is
measured. The powder is loaded into a cylinder and the surface levelled. A 50 g plastic disc is placed on top of the powder and a 10 kg weighted plunger is placed slowly on top of the disc and allowed to remain in position for 2 minutes. The weight and plunger are then removed and the cylinder removed carefully from the powder to leave a free-standing cylinder of powder with the 50g plastic disc on top of it. If the compact is unbroken, a second 50 g plastic disc is placed on top of the first and left for approximately ten seconds. Then if the compact is still unbroken a 100 g disc is added to the plastic discs and left for ten seconds. The weight is then increased in 0.25 kg increments at 10 second intervals until the compact collapses. The total weight (w) needed to effect collapse is noted .
The cohesiveness of a powder is classified by the weight (w) as follows : w < 1.0 kg Good flowing 1.0 kg < w < 2.0 kg Moderate flowing. 2.0 kg < w < 5.0 kg Cohesive. 5.0 kg < w Very cohesive.
Dissolution time (T90)
A 1-litre beaker is filled with 500mls of demineralised water at 20-25°C and stirred with a magnetic stirrer adjusted to give a vortex of about 4cm. A sample of powder is added to the water. The dissolution is measured according to solution conductivity. The T90' value is the time taken to achieve 90% of the final conductivity value.
Bulk density (BP)
This is measured by taking the increase in weight of a 1 litre container when it is filled with detergent granules and tapped lightly .
The invention will now be further described by way of the following non limiting examples.
EXAMPLES HMC 1 - Spray dried HMC (low moisture) - (Example 1 from
PCT/EP2009/054757
HMC was prepared according to WO 2006/081930 Al by mixing together 29.8 kg of Sokalan CP5 solution (40% active material)
with 1373.8kg of water in a stirred tank. Into this solution was then dissolved 596.4 kg of light Sodium Carbonate (ex
Brunner Mond) . The resultant solution was then spray dried in a 2.5 m diameter spray-drying tower to a final product moisture content of 1.8 % (by IR Balance) .
Example 2
1337g of spray dried product from example 1 was mixed with 3.76g CBS-X fluorescer powder and 15.68g powdered SCMC in the bowl of a Zanchetta RotoJunior (10 litre) mixer/ granulator. The mixer was operated with a rotor speed of 350 rpm and a chopper speed of 1350 rpm. To the mixing powder was then added a blend of LAS acid (470g) and 30EO Nonionic surfactant
(125.4g) , over a period of approximately 3 minutes. The
resulting product was a free flowing powder with a nominal composition :
Component wt%
Sodium Carbonate 63.56
Sokalan CP5 1.35
NaLAS 26.16
NI (30EO) 6.53
CBS-X 0.20
SCMC 0.82
Water 1.38
Measured powder properties were very good.
BD = 704
DFR = 146
UCT = 0
Mean size about 400 microns.
% >1400micron = 0.17
% < 180 micron = 3.48 T90 approximately 60 seconds. Example 3
50g of spray dried product from example 1 was mixed with 0.14g CBS-X fluorescer powder and 0.59g powdered SCMC in the bowl of a Braun MR 500 CA Mixer. To the mixing powder was then added a blend of LAS acid (16g) and 30EO Nonionic surfactant (4.27g), over a period of approximately 2 minutes. The resulting product was a free flowing powder with nominal composition:
Component wt%
Sodium Carbonate 65.65
Sokalan CP5 1.39
NaLAS 24.46
NI (30EO) 6.11
CBS-X 0.20
SCMC 0.84
Water 1.36
Example 4
50g of spray dried product from example 1 was mixed with 0.165g CBS-X fluorescer powder and 0.63g powdered SCMC in the bowl of a Braun MR 500 CA Mixer. To the mixing powder was then added a blend of LAS acid (20g) and 30EO Nonionic surfactant (5.34g), over a period of approximately 2 minutes. The resulting product was a free flowing powder with nominal composition: Component wt%
Sodium Carbonate 60.49
Sokalan CP5 1.30
NaLAS 28.58
NI (30EO) 7.14
CBS-X 0.22
SCMC 0.84
Water 1.42
Example 5
50g of spray dried product from example 1 was mixed with 0.165g CBS-X fluorescer powder and 0.67g powdered SCMC in the bowl of a Braun MR 500 CA Mixer. To the mixing powder was then added a blend of LAS acid (24g) and 30EO Nonionic surfactant (6.41g), over a period of approximately 2 minutes. The resulting product was a free flowing powder with nominal composition:
Component wt%
Sodium Carbonate 55.99
Sokalan CP5 1.22
NaLAS 32.22
NI (30EO) 8.05
CBS-X 0.21
SCMC 0.84
Water 1.47
Example 6
50g of spray dried product from example 1 was mixed with 0.13g CBS-X fluorescer powder and 0.56g powdered SCMC in the bowl of a Braun MR 500 CA Mixer. To the mixing powder was then added a blend of LAS acid (13g) and 30EO Nonionic surfactant (3.47g), over a period of approximately 2 minutes. The resulting product was a free flowing powder with nominal composition:
Component wt%
Sodium Carbonate 69.99
Sokalan CP5 1.46
NaLAS 20.96
NI (30EO) 5.23
CBS-X 0.20
SCMC 0.85
Water 1.30
Example 7
50g of spray dried product from example 1 was mixed with 0.56g powdered SCMC in the bowl of a Braun MR 500 CA Mixer. To the mixing powder was then added a blend of LAS acid (20g) and 30EO Nonionic surfactant (5.34g), over a period of approximately 2 minutes. The resulting product was a free flowing powder with nominal composition: Component wt%
Sodium Carbonate 60.63
Sokalan CP5 1.30
NaLAS 28.65
NI (30EO) 7.16
CBS-X 0.0
SCMC 0.84
Water 1.42
Example 8
50g of spray dried product from example 1 was mixed with 0.13g CBS-X fluorescer powder and 0.56g powdered SCMC in the bowl of a Braun MR 500 CA Mixer. To the mixing powder was then added a blend of LAS acid (18g) and 30EO Nonionic surfactant (2.14g), over a period of approximately 2 minutes. The resulting product was a free flowing powder with nominal composition:
Component wt%
Sodium Carbonate 65.42
Sokalan CP5 1.39
NaLAS 27.62
NI (30EO) 3.07
CBS-X 0.20
SCMC 0.85
Water 1.44 Example 9
50g of spray dried product from example 1 was mixed with 0.13g CBS-X fluorescer powder and 0.56g powdered SCMC in the bowl of a Braun MR 500 CA Mixer. To the mixing powder was then added a blend of LAS acid (18g) and 30EO Nonionic surfactant (2.14g), over a period of approximately 2 minutes. The resulting product was a free flowing powder with nominal composition:
Component wt%
Sodium Carbonate 65.89
Sokalan CP5 1.38
NaLAS 21.32
NI (30EO) 9.14
CBS-X 0.19
SCMC 0.80
Water 1.27
Example 10
50g of spray dried product from example 1 was mixed with 0.13g CBS-X fluorescer powder and 0.56g powdered SCMC in the bowl of a Braun MR 500 CA Mixer. To the mixing powder was then added a blend of LAS acid (18g) and 7EO Nonionic surfactant (2.14g), over a period of approximately 2 minutes. The resulting product was a free flowing powder with nominal composition:
Component wt%
Sodium Carbonate 65.89
Sokalan CP5 1.38
NaLAS 21.32
NI (7EO) 9.14
CBS-X 0.19
SCMC 0.80
Water 1.27
Claims
A detergent granule comprising:
a) from 25 wt% to 45 wt% surfactant, comprising linear alkylbenzene sulphonic acid neutralised with habit modified carbonate to form sodium LAS and an ethoxylated nonionic surfactant having a degree of ethoxylation of from 5 to 50EO (NI), the granule having a LAS/NI ratio of from 90:10 to 70:30, preferably from 85:15 to 75:25, b) at least 20wt% habit modified Sodium Carbonate, which is a crystal growth modified Sodium Carbonate that comprises a mixture of Sodium Carbonate and polymer, and c) less than 10 wt%, preferably zero, zeolite, less than lwt%, preferably zero phosphate, e) 0.2 wt% to 4 wt% Sodium carboxymethyl cellulose (SCMC) obtainable by a process comprising the dry neutralisation of liquid LAS acid with habit modified Sodium Carbonate, wherein the LAS acid is reacted while mixing with a molar excess of habit modified Sodium Carbonate to form Sodium LAS, while mixing.
Detergent granule according to claim 1 wherein the NI is an alkyl ethoxylate with a degree of ethoxylation of from 25EO to 35EO, preferably 30EO and the granule comprises (wt %) :
LAS 25 - 34
NI 25-35EO 2.9 - 7.5
Habit Modified Carbonate 20-67, preferably 56 - 67
SCMC 0.2 - 4
Water and minors balance
Detergent granule according to claim 1 wherein the NI is an alkyl ethoxylate with a degree of ethoxylation of from 5EO to 9EO and the granule comprises (wt %) :
LAS 22 - 30
NI 5-9EO 5.5 - 11.5
HMC 20 - 67, preferably 56 - 57
SCMC 0.2 - 4
Water and minors balance
The ratio of LAS:NI preferably lying in the range 80:20 to 70:30.
Detergent granule according to any preceding claim wherein the process is carried out by mixing in a mixer with a chopping or cutting action and the chopping or cutting action is used during the dry neutralisation reaction.
Detergent granule according to claim 4 in which the mixing is carried out in a mixer, which has both a stirring action and a chopping or cutting action, and both actions are used during the dry neutralisation reaction.
Detergent granule according to any preceding claim in which the neutralising agent comprises a mixture of habit modified carbonate and habit modified Burkeite.
Detergent granule according to any preceding claim in which the habit modified Sodium Carbonate is characterised by having a specific surface area of 5 m2/g or greater, preferably 8 m2/g or greater, even more preferably 10 m2/g or greater.
8. Detergent granule according to claim 7 in which the habit modified Sodium Carbonate is characterised by having a pore volume, in pores less than 2 micron diameter, of 0.3 ml/g or greater.
9. Detergent granule according to any preceding claim
characterised in that the surfactant level in the granule is greater than 27 wt%, preferably greater than 28 wt%, even greater than 30 wt% and preferably even greater than 34 wt%.
10. Detergent granule according to any preceding claim,
further comprising perfume.
11. Detergent granule according to any preceding claim,
further comprising soap.
Detergent granule according to any preceding claim further comprising fluorescer, preferably at a level of 0.05 to 0.5 wt% .
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EP2740786A1 (en) | 2012-12-06 | 2014-06-11 | Solvay SA | Process for preparing detergent composition particles |
WO2014172902A1 (en) * | 2013-04-26 | 2014-10-30 | The Procter & Gamble Company | Detergent granules with a water-swellable component |
CN105164242A (en) * | 2013-04-26 | 2015-12-16 | 宝洁公司 | Detergent granules with water-swellable component |
WO2015189248A1 (en) * | 2014-06-10 | 2015-12-17 | Solvay Sa | Process for the production of detergent composition particles |
EP3075831A1 (en) * | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
WO2017190300A1 (en) * | 2016-05-05 | 2017-11-09 | The Procter & Gamble Company | Cleaning compositions |
US9951296B2 (en) | 2015-03-30 | 2018-04-24 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
US9951301B2 (en) | 2015-03-30 | 2018-04-24 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
US9957470B2 (en) | 2015-03-30 | 2018-05-01 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
US9957466B2 (en) | 2015-03-30 | 2018-05-01 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
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CN104968775A (en) * | 2012-12-06 | 2015-10-07 | 索尔维公司 | Process for preparing detergent composition particles |
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CN105164242A (en) * | 2013-04-26 | 2015-12-16 | 宝洁公司 | Detergent granules with water-swellable component |
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WO2016160870A1 (en) * | 2015-03-30 | 2016-10-06 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
EP3075831A1 (en) * | 2015-03-30 | 2016-10-05 | The Procter and Gamble Company | Solid free-flowing particulate laundry detergent composition |
US9951296B2 (en) | 2015-03-30 | 2018-04-24 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
US9951301B2 (en) | 2015-03-30 | 2018-04-24 | The Procter & Gamble Company | Solid free-flowing particulate laundry detergent composition |
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