EP1141197B1 - Verfahren zur herstellung eines granularen waschmittels enthaltend eine modifizierte carboxymethylcellulose - Google Patents
Verfahren zur herstellung eines granularen waschmittels enthaltend eine modifizierte carboxymethylcellulose Download PDFInfo
- Publication number
- EP1141197B1 EP1141197B1 EP99966543A EP99966543A EP1141197B1 EP 1141197 B1 EP1141197 B1 EP 1141197B1 EP 99966543 A EP99966543 A EP 99966543A EP 99966543 A EP99966543 A EP 99966543A EP 1141197 B1 EP1141197 B1 EP 1141197B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent
- agglomerates
- densifier
- density
- speed mixer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003599 detergent Substances 0.000 title claims description 213
- 239000000203 mixture Substances 0.000 title claims description 92
- 238000000034 method Methods 0.000 title claims description 79
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims description 32
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims description 32
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims description 32
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims description 32
- 229940105329 carboxymethylcellulose Drugs 0.000 title claims description 32
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 title claims description 26
- 239000000463 material Substances 0.000 claims description 70
- 239000008187 granular material Substances 0.000 claims description 47
- 239000004094 surface-active agent Substances 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 45
- 239000011230 binding agent Substances 0.000 claims description 43
- -1 polymaleates Polymers 0.000 claims description 33
- 239000004615 ingredient Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 29
- 229920001577 copolymer Polymers 0.000 claims description 25
- 239000011734 sodium Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229920001519 homopolymer Polymers 0.000 claims description 18
- 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 description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 17
- 239000003945 anionic surfactant Substances 0.000 claims description 15
- 238000001694 spray drying Methods 0.000 claims description 13
- 239000002736 nonionic surfactant Substances 0.000 claims description 12
- 229920000058 polyacrylate Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 150000001204 N-oxides Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000003093 cationic surfactant Substances 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920003232 aliphatic polyester Polymers 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 229920001308 poly(aminoacid) Polymers 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 102000004169 proteins and genes Human genes 0.000 claims description 4
- 108090000623 proteins and genes Proteins 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 30
- 125000004432 carbon atom Chemical group C* 0.000 description 28
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 21
- 239000002245 particle Substances 0.000 description 20
- 239000004744 fabric Substances 0.000 description 18
- 238000005054 agglomeration Methods 0.000 description 17
- 230000002776 aggregation Effects 0.000 description 17
- 239000012530 fluid Substances 0.000 description 16
- 238000005342 ion exchange Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 8
- 150000008051 alkyl sulfates Chemical class 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 150000004760 silicates Chemical class 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000000280 densification Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000004900 laundering Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006677 Appel reaction Methods 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000008233 hard water Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 238000013178 mathematical model Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005192 alkyl ethylene group Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 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
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
Definitions
- the present invention generally relates to processes for producing a granular detergent composition. More particularly, the invention is directed to processes during which detergent granules or agglomerates are produced from starting detergent materials, one of which is a modified carboxy methyl cellulose.
- formulators In an effort to appease consumers' desires to slow, or preferably, eliminate the degradation of a fabric's appearance, formulators have searched for detergent additives that will aid in maintaining a fabric's appearance over its normal life cycle. As new detergent additives are developed, formulators must find a way to incorporate the additives into detergent compositions without adversely affecting the physical or chemical properties of the existing composition. That is, an additive that maintains fabric appearance should not reduce the cleaning efficacy of the detergent, nor should it cause the detergent to clump or otherwise have undesirable physical characteristics in the eyes of the average consumer. Often, the challenges associated with the introduction of a new detergent additive can be met with adjustments to the detergent manufacturing process.
- the first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules.
- the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant.
- a binder such as a nonionic or anionic surfactant.
- surfactants and combinations thereof in detergent compositions.
- various anionic surfactants especially the alkyl benzene sulfonates, alkyl sulfates, alkyl alkoxy sulfates and various nonionic surfactants, such as alkyl ethoxylates and alkylphenol ethoxylates are commonly used in detergent formulations.
- Surfactants have found use as detergent components capable of the removal of a wide variety of soils and stains. A consistent effort, however, is made by detergent manufacturers to improve detersive properties of detergent compositions by providing new and improved surfactants.
- a problem commonly associated with anionic surfactants is their sensitivity to cold water and/or hard water.
- the present invention meets the aforementioned needs in the art by providing a process for continuously preparing detergent agglomerates comprising the steps of: (A) continuously mixing a liquid binder and dry detergent materials into a high speed mixer/densifier to obtain detergent agglomerates, wherein the ratio of the liquid binder to the dry detergent material is from 1:10 to 10:1, wherein the dry detergent materials comprise modified carboxy methyl cellulose; (B) optionally mixing the detergent agglomerates in a moderate speed mixer/densifier to further density and agglomerate the detergent agglomerates; and (C) drying the detergent agglomerates so as to increase their density.
- the dry detergent materials consist essentially of modified carboxy methyl cellulose.
- the liquid binder comprises water and a polymer selected from the group consisting of dye transfer agents, polyamines, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrolidone, polymaleates, aliphatic polyesters, natural proteins, synthetic non-crystalline polyaminoacids, water soluble nylons, polyethylene glycol, polyacrylate and mixtures thereof.
- the liquid binder comprises a polymer selected from the group consisting of a polyvinyl N-Oxide, a copolymer of epichlorohydrin and a cyclic amine moiety, and mixtures thereof.
- a preferred aspect of the invention includes the use of a surfactant paste in addition to the polymer-based liquid binder.
- the paste includes surfactants selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
- the surfactant paste is selected from the group consisting of linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C 11-13 LAS, Sodium ethoxysulphate based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene oxide.
- second detergent agglomerates can be made by a process comprising the steps of: (A) continuously mixing a detergent surfactant paste and additional dry detergent materials into a high speed mixer/densifier to obtain second detergent agglomerates, wherein the ratio of the surfactant paste to the additional dry detergent material is from 1:10 to 10:1; (B) optionally mixing the second detergent agglomerates in a moderate speed mixer/densifier to increase their density; (C) drying the second detergent agglomerates to further increase their density.
- the second detergent agglomerates can then be mixed with the first detergent agglomerates to form the high density detergent composition.
- the surfactant paste can be replaced by, or supplemented with an acid precursor of an anionic surfactant and additional dry detergent materials which contain an alkaline inorganic material capable of neutralizing the acid precursor.
- detergent granules can be admixed with the modified carboxy methyl cellulose containing agglomerates defined above to form a high density detergent composition.
- These granules can be formed by spray drying an aqueous slurry containing adjunct detergent ingredients to form spray dried granules. Then the granules and the detergent agglomerates can be blended together to form the high density detergent composition.
- modified carboxy methyl cellulose materials provide fabric appearance benefits.
- the modified carboxy methyl cellulose materials are sometimes supplied as a sticky powder, which when added to a detergent composition can cause the resulting detergent agglomerates to be sticky as well.
- Sticky agglomerates often cause clumps in the detergent composition which is a strong consumer negative.
- these modified carboxy methyl cellulose materials are not always dispersed satisfactorily, resulting in reduced performance and moreover localised residues of the material in the washing machine and on the fabrics.
- other detergent ingredients can become entrapped in the cellulosic material, causing further residue problems, reduced performance of these other ingredients.
- the stickiness and the poor dispersability of the modified carboxy methyl cellulose, and its deleterious effect on the detergent composition can be counter-acted by the processing conditions and constituents defined herein.
- a first agglomerate is prepared from using a liquid binder comprising a mixture of surfactant selected from the group of LAS, preferably C 11-13 LAS or Sodium ethoxysulphate, wherein the ethoxysulate is preferably based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene oxide and mixtures thereof; this liquid binder is used in combination with a polymer selected from the group of a copolymer of epichlorohydrin and a cyclic amine moiety or polyvinyl N-Oxide, and mixtures thereof in combination with dry detergent materials that include a modified carboxy methyl cellulose.
- a liquid binder comprising a mixture of surfactant selected from the group of LAS, preferably C 11-13 LAS or Sodium ethoxysulphate, wherein the ethoxysulate is preferably based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate
- a second agglomerate is prepared using a surfactant paste and dry starting materials that do not include modified carboxy methyl cellulose.
- the two separate agglomerates are admixed to form a detergent composition that is free flowing.
- the separate detergent particles of this invention can be formed by spray drying techniques which can include further processing of the "post-tower" detergent granules.
- post-tower detergent granules it is meant those detergent granules which have been processed through a conventional spray-drying tower or. similar apparatus.
- compositions of the invention contain, in addition to a modified carboxy methyl cellulose material, at least one suitable adjunct dry detergent ingredient which is preferably included in the detergent composition.
- the resulting detergent composition preferably comprises from 0.01% to 4%, more preferably from 0.05% to 2%, and most preferably from 0.1% to 1%, by weight of the modified carboxy methyl cellulose.
- the adjunct dry detergent ingredient is preferably selected from the group consisting of builders, enzymes, bleaching agents, bleach activators, suds suppressors, soil release agents, brighteners, perfumes, hydrotropes, dyes, pigments, polymeric dispersing agents, pH controlling agents, chclants, processing aids, crystallization aids, and mixtures thereof.
- the following disclosure of modified carboxy methyl cellulose materials and adjunct detergent ingredients and mixtures thereof for use in the compositions herein is representative of the detergent ingredients, but is not intended to be limiting.
- modified carboxy methyl cellulose materials which are in the form of cellulosic based polymers or oligomers, can provide substantive and unexpected cleaning benefits when added to a laundry composition. But these materials can also pose certain processing problems for granular detergent formulators.
- the modified carboxy methyl cellulose materials that are suitable for use in laundry operations and provide the desired fabric appearance and integrity benefits can be characterized by the following general formula: wherein each R is selected from the group consisting of R 2 , R c , and wherein:
- carboxy methyl cellulose is modified with an ester linkage, ether linkage or combinations thereof.
- Modified carboxy methyl cellulose materials suitable for use in this invention are described in greater detail in two applications entitled “Laundry Detergent Compositions With Cellulosic Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith", WO 99/14245 and WO 99/14295. Both of these applications were filed in the PCT on September 15, 1998, in the name of Jennifer A. Leupin et al.
- One or more builders can be used to further improve the performance of the compositions described herein.
- the builder can be selected from the group consisting of aluminosilicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates and mixtures thereof.
- the sodium carbonate ingredient can serve as the inorganic alkaline material when a liquid acid precursor of the mid-chain branched surfactant is used.
- suitable auxiliary builders are described hereinafter.
- Preferred builders include aluminosilicate ion exchange materials and sodium carbonate.
- the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced.
- the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble).
- the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit as high of an exchange rate and capacity as provided by the sodium form.
- the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
- the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
- the term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
- the preferred particle size diameter of the aluminosilicate is from 0.1 micron to 10 microns, more preferably from 0.5 microns to 9 microns. Most preferably, the particle size diameter is from 1 microns to 8 microns.
- the aluminosilicate ion exchange material has the formula Na z [(AlO 2 ) z .(SiO 2 ) y ]xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is from 1 to 5 and x is from 10 to 264. More preferably, the aluminosilicate has the formula Na 12 [(AlO 2 ) 12 .(SiO 2 ) 12 ]xH 2 O wherein x is from 20 to 30, preferably about 27.
- These preferred aluminosilicatcs are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
- naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669.
- the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO 3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/-gram/gallon, and more preferably in a range from 2 grains Ca ++ /gallon/minute/-gram/gallon to 6 grains Ca ++ /gallon/minute/-gram/gallon.
- the dry starting materials are mixed with a liquid binder.
- a binder is added for purposes of enhancing agglomeration by providing a "binding" or “sticking” agent for the detergent components.
- the preferred liquid binder for use in this invention comprises water, surfactant paste and a polymer.
- the paste includes surfactants selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. The viscosity, rheology and chemical composition of the surfactant pastes are described in more detail below.
- the polymer is selected from the group consisting of dye transfer agents, polyamines, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrolidone, polymaleates, aliphatic polyesters, natural proteins, synthetic non-crystalline polyaminoacids, water soluble nylons, polyethylene glycol, polyacrylate and mixtures thereof.
- Detergent compositions made with the agglomerates of this invention preferably comprise from 0.01% to 4%, more preferably from 0.05% to 2%, and most preferably from 0.1% to 1%, by weight of the liquid binder.
- the surfactant paste is selected from the group consisting of linear straight chain alkylbenzene sulfonates, preferably linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13 (abbreviated as C 11-13 LAS), sodium ethoxysulphate, preferably based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene oxide, and mixtures thereof.
- the dye transfer agent is a polyvinyl N-Oxide such as poly(4-vinylpyridine-N-oxide) "PVNO".
- PVNO poly(4-vinylpyridine-N-oxide)
- Copolymers of N-vinylpyrrolidone and N-vinylimidazole are also acceptable for use herein.
- Polyvinyl N-oxide materials are disclosed in U.S. Patent No. 5,804,543, which issued on September 8, 1998, to Wertz and Panandiker.
- liquid binders for use in this invention are polyamines, and even more preferred are copolymers of epichlorohydrin and a cyclic amine moiety. Descriptions and example of the preferred polyamines for use in this invention can be found in the following PCT Patent Applications: WO 99/14300, WO 99/14299 and WO 99/14301 all three of these applications were filed internationally on September 15, 1988.
- the process comprises the step of spraying an additional binder in one or both of the mixer/densifiers.
- the additional binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof.
- suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble Co.).
- the viscoelastic surfactant paste used herein has viscoelastic fluid properties which can be described by a commonly used mathematical model that accounts for the shear thinning nature of the paste.
- the rate index n varies from 0 to 1. The closer n is to 0, the more shear thinning the fluid. The closer n is to 1, the closer it is to simple Newtonian behavior, i.e. constant viscosity behavior. K can be interpreted as the apparent viscosity at a shear rate of 1 sec -1 .
- the viscoelastic surfactant paste used in the process has a consistency K at 70°C of from 50,000 to 450,000 cPoise ⁇ sec n-1 (500 to 2,500 Poise ⁇ sec n-1 ), more preferably from 100,000 to 195,000 cPoise ⁇ sec n-1 (1,000 to 1,950 Poise ⁇ sec n-1 ), and most preferably from 120,000 to 180,000 cPoise ⁇ sec n-1 (1,200 to 1,800 Poise ⁇ sec n-1 ).
- the surfactant paste has a shear index n of from 0.05 to 0.25, more preferably from 0.08 to 0.20 and most preferably from 0.10 to 0.15.
- the paste includes surfactants selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
- Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975.
- Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980.
- detergent surfactants useful in the present surfactant paste.
- Water-soluble salts of the higher fatty acids i.e., "soaps" are useful anionic surfactants in the compositions herein.
- Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
- Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
- Additional anionic surfactants that are suitable for use herein include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure a straight-chain alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8-18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
- Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C 11-13 LAS.
- anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
- suitable anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; water-soluble salts of olefin and paraffin sulfonates containing from 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
- Preferred adjunct anionic surfactants are C 10-18 linear alkylbenzene sulfonate and C 10-18 alkyl sulfate.
- low moisture (less than about 25% water) alkyl sulfate paste can be the sole ingredient in the surfactant paste.
- Most preferred are C 10-18 alkyl sulfates, linear or branched, and any of primary, secondary or tertiary.
- a preferred embodiment of the present invention is wherein the surfactant paste comprises from 20% to 40% of a mixture of sodium C 10-13 linear alkylbenzene sulfonate and sodium C 12-16 alkyl sulfate in a weight ratio of about 2:1 to 1:2.
- Another preferred embodiment of the detergent composition includes a mixture of C 10-18 alkyl sulfate and C 10-18 alkyl ethoxy sulfate in a weight ratio of about 80:20.
- Water-soluble nonionic surfactants are also useful in the instant invention.
- Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
- the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl phenol. Included are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.
- nonionics suitable for use herein are semi-polar nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
- Preferred nonionic surfactants are of the formula R 1 (OC 2 H 4 ) n OH, wherein R 1 is a C 10 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group, and n is from 3 to about 80.
- Particularly preferred are condensation products of C 12 -C 15 alcohols with from 5 to 20 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
- Nonionic surfactants include polyhydroxy fatty acid amides. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Patent No. 2,965,576 and Schwartz, U.S. Patent No. 2,703,798.
- Ampholytic surfactants include derivatives of aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
- Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from 8 to 18 carbon atoms.
- Cationic surfactants can also be included in the present invention.
- Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than about 8.5. A more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
- Cationic surfactants are often used in detergent compositions to provide fabric softening and/or antistatic benefits.
- Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976.
- agglomerates refers to particles formed by build-up agglomeration of starting detergent ingredients (particles) which typically have a smaller median particle size than the formed agglomerates. All percentages and ratios used herein are expressed as percentages by weight (anhydrous basis) unless otherwise indicated. All viscosities referenced herein are measured at 70°C ( ⁇ 5°C) and at shear rates of about 10 to 100 sec -1 .
- the invention entails continuously mixing into a high speed mixer/densifier several streams of starting detergent ingredients which include a liquid binder comprising a mix of a liquid polymer and a surfactant paste. Dry detergent materials, which may include a modified carboxy methyl cellulose material, are also added continuously into the high speed mixer/densifier.
- the dry starting detergent material comprises from 10% to 50%, preferably from 15% to 45% and, most preferably from 20% to 40% of an aluminosilicate or zeolite builder and from 10% to 40%, preferably from 15% to 30% and, most preferably from 15% to 25% of a sodium carbonate. It should be understood that additional starting detergent ingredients several of which are described hereinafter may be mixed into high speed mixer/densifier without departing from the scope of the invention.
- the dry starting detergent material comprises from 10% to 50%, preferably from 15% to 45% and, most preferably from 20% to 40% of an aluminosilicate or zeolite builder and from 10% to 40%, preferably from 15% to 30% and, most preferably from 15% to 25% of an ester modified carboxy methyl cellulose. It should be understood that additional starting detergent ingredients several of which are described hereinafter may be mixed into high speed mixer/densifier without departing from the scope of the invention.
- the ratio of the surfactant paste or liquid binder to the dry starting detergent material is from 1:10 to 10:1, more preferably from 1:4 to 4:1 and, most preferably from 2:1 to 2:3.
- the first processing step can be successfully completed, under the process parameters described herein, in a high speed mixer/densifier which preferably is a Lödige CB mixer or similar brand mixer.
- a high speed mixer/densifier which preferably is a Lödige CB mixer or similar brand mixer.
- These types of mixers essentially consist of a horizontal, hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached.
- the shaft rotates at a speed of from 300 rpm to 2500 rpm, more preferably from 400 rpm to 1600 rpm.
- the mean residence time of the detergent ingredients in the high speed mixer/densifier is preferably in range from 2 seconds to 45 seconds, and most preferably from 5 seconds to 15 seconds.
- the mean residence time can be conveniently and accurately measured by dividing the tear weight of the mixer/densifier by the throughput (e.g., kg/hr).
- the resulting detergent agglomerates formed in the high speed mixer/densifier are then fed into a lower or moderate speed mixer/densifier during which further agglomeration and densification is carried forth.
- This particular moderate speed mixer/densifier used in the present process should include liquid distribution and agglomeration tools so that both techniques can be carried forth simultaneously. It is preferable to have the moderate speed mixer/densifier to be, for example, a Lödige KM (Ploughshare) mixer, Drais® K-T 160 mixer or similar brand mixer.
- the main centrally rotating shaft speed is from 30 to 160 rpm, more preferably from 50 to 100 rpm.
- the mean residence time in the moderate speed mixer/densifier is preferably from 0.25 minutes to 15 minutes, most preferably the residence time is 0.5 to 10 minutes.
- This mean residence time also can be conveniently and accurately measured by dividing the tear weight of the mixer/densifier at steady state by the throughput (e.g., kg/hr).
- the liquid distribution is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm.
- the high speed mixer/densifier and moderate speed mixer/densifier in combination preferably impart a requisite amount of energy to form the desired agglomerates. More particularly, the instant process imparts from 5 ⁇ 10 10 erg/kg to 2 ⁇ 10 12 erg/kg at a rate of from 3 ⁇ 10 8 erg/kg-sec to 3 ⁇ 10 9 erg/kg-sec to form free flowing high density detergent agglomerates.
- the energy input and rate of input can be determined by calculations from power readings to the moderate speed mixer/densifier with and without granules, residence time of the granules in the mixer/densifier, and the mass of the granules in the mixer/densifier. Such calculations are clearly within the scope of the skilled artisan.
- the detergent agglomerates are dried in a fluid bed dryer or similar apparatus.
- the density of the resulting detergent agglomerates exiting the fluid bed dryer is at least 400 g/l, more preferably from 500 g/l to 600 g/l.
- the particle porosity of the resulting detergent agglomerates of the composition is preferably in a range from 5% to 20%, more preferably at about 10%.
- a low porosity detergent agglomerate provides a dense or low dosage detergent product, to which the present process is primarily directed.
- an attribute of dense or densified detergent agglomerates is the relative particle size.
- the present process typically provides agglomerates having a median particle size of from 400 microns to 700 microns, and more preferably from 475 microns to 600 microns.
- the phrase "median particle size" refers to individual agglomerates and not individual particles or detergent granules.
- the detergent agglomerates exiting the fluid bed dryer are further conditioned by cooling the agglomerates in a fluid bed cooler or similar apparatus as are well known in the art.
- Another optional process step involves adding a coating agent to improve flowability and/or minimize over agglomeration of the detergent composition in one or more of the following locations of the instant process: (I) the coating agent can be added directly after the fluid bed cooler; (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler; (3) the coating agent may be added between the fluid bed dryer and the moderate speed mixer/densifier; and/or (4) the coating agent may be added directly to the moderate speed mixer/densifier and the fluid bed dryer.
- the coating agent can be added in any one or a combination of streams, see Capeci et al, U.S. Patent 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued February 6, 1996.
- the coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof.
- the coating agent may be one or more combinations of the builder material, aluminosilicates, carbonates, silicates.
- the coating agent not only enhances the free flowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping of detergent during use, but also serves to control agglomeration by preventing or minimizing over agglomeration, especially when added directly to the moderate speed mixer/densifier. As those skilled in the art are well aware, over agglomeration can lead to very undesirable flow properties and aesthetics of the final detergent product.
- optional steps contemplated by the present process include screening the oversized detergent agglomerates in a screening apparatus which can take a variety of forms including but not limited to conventional screens chosen for the desired particle size of the finished detergent product.
- Other optional steps include conditioning of the detergent agglomerates by subjecting the agglomerates to additional drying.
- Another optional step of the instant process entails finishing the resulting detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients.
- this step encompasses spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition.
- Such techniques and ingredients are well known in the art.
- One or more spray drying techniques can be used alone, or in combination with the aforementioned agglomeration processes, to make detergent compositions in accordance with the instant invention.
- One or more spray-drying towers may be employed to manufacture granular laundry detergents which often have a density of about 500 g/l or less.
- an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drying tower, using conventional techniques, at temperatures of 175°C to 225°C.
- additional process steps as described herein can be optionally used to obtain the level of density (i.e., > 650 g/l) required by modern compact, low dosage detergent products.
- spray-dried granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers.
- a suitable high speed mixer/densifier for this process is the aforementioned "Lödige CB 30" or “Lödige CB 30 Recycler” which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon.
- the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification. See Jacobs et al, U.S. Patent 5,149,455, issued September 22, 1992.
- Other such apparatus includes the devices marketed under the trade name "Shugi Granulator” and under the tradename "Drais K-TTP 80.”
- Another process step which can be used to densify further spray-dried granules involves grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer/densifier so as to obtain particles having lower porosity.
- Equipment such as the aforementioned "Lödige KM" (Series 300 or 600) or “Lödige Ploughshare” mixer/densifiers are suitable for this process step.
- Other useful equipment includes the device which is available under the tradename "Drais K-T 160".
- This process step which employs a moderate speed mixer/densifier e.g. Lödige KM
- the aforementioned high speed mixer/densifier e.g. Lödige CB
- Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942.
- the reverse sequential mixer/densifier configuration is also contemplated by the invention.
- One or a combination of various parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dried granules in the process of the invention.
- adjunct ingredients such as liquid binders and flow aids
- Patent 5,133,924, issued July 28, 1992 spray-dried granules are brought into a deformable state prior to densification
- Delwel et al U.S. Patent 4,637,891, issued January 20, 1987 (granulating spray-dried granules with a liquid binder and aluminosilicate); Kruse et al, U.S. Patent 4,726,908, issued February 23, 1988 (granulating spray-dried granules with a liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Patent 5,160,657, issued November 3, 1992 (coating densified spray-dried granules with a liquid binder and aluminosilicate).
- other aspects of the process invention include admixing additional detergent materials with the various agglomerates, spray dried granules and combinations thereof.
- This admixing step may be enhanced by combining the agglomerates, granules, or combinations thereof with additional detergent materials and a liquid binder in a mixing drum or other similar device.
- the additional detergent materials may be coated with a nonionic surfactant or other liquid binder as described previously before the admixing step so as to preclude any deleterious interaction with the other detergent ingredients (e.g. anionic surfactants) prior to immersion in the washing solution (i.e. during processing and storage).
- This liquid binder or nonionic surfactant coating also improves the flow properties of the detergent composition in which the builder material is included.
- the high density detergent composition can be produced by feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form agglomerates containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients. Subsequently, the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e.g. Lödige KM) for further agglomeration resulting in the finished high density detergent composition.
- a moderate speed mixer/densifier e.g. Lödige KM
- the surfactant paste is premixed or extruded in a mixing or extruding apparatus such as a twin-screw extruder (e.g., Werner and Pfleiderer, Continua Series) to structure the paste for easier agglomeration.
- a mixing or extruding apparatus such as a twin-screw extruder (e.g., Werner and Pfleiderer, Continua Series) to structure the paste for easier agglomeration.
- structuring agents such as polymers, sodium hydroxide, sodium chloride, potassium hydroxide silicates can be used to render the paste more suitable for loading higher amounts of surfactant. See Aouad et al, U.S. Patent 5,451,354, issued September 19, 1995.
- high density detergent compositions can be produced by blending conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (e.g. a 60:40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein.
- Additional adjunct ingredients such as enzymes, perfumes, brighteners can be sprayed or admixed with the agglomerates, granules or mixtures thereof produced by the processes discussed herein.
- Another process of the invention involves cooling a molten surfactant paste and forming flakes on a chill roll, after which the flakes are ground to the desired particle size.
- the cooled flakes can be dried further using a rotary drum dryer.
- This Example illustrates the process of the invention which produces free flowing, crisp, high density detergent composition.
- Two feed streams of various detergent starting ingredients are continuously fed, at a rate of 2800 kg/hr, into a Lödige CB-30 mixer/densifier.
- One stream comprises a liquid binder containing water and PVNO the other stream containing dry detergent materials containing an ester modified carboxy methyl cellulose, aluminosilicate and sodium carbonate.
- the rotational speed of the shaft in the Lödige CB-30 mixer/densifier is about 1400 rpm and the mean residence time is about 10 seconds.
- the contents from the Lödige CB-30 mixer/densifer are continuously fed into a Lödige KM 600 mixer/densifer for further agglomeration during which the mean residence time is about 30 seconds.
- the resulting detergent agglomerates are then fed to a fluid bed dryer and then to a fluid bed cooler, the mean residence time being about 10 minutes and 15 minutes, respectively.
- a coating agent, aluminosilicate, is fed after the Lödige KM 600 mixer/densifier to control and prevent over agglomeration.
- the detergent agglomerates are then screened with conventional screening apparatus resulting in a uniform particle size distribution.
- composition of the detergent agglomerate mixture exiting the fluid bed cooler for three process runs are set forth in Table I below: Component % Weight of Total Feed A B C Ester Modified Carboxy Methyl Cellulose 5.0 5.0 3.0 PVNO 36.0 41.0 22.0 Aluminosilicate 25.4 24.0 34.0 Sodium carbonate 26.3 24.0 34.0 Polyethylene glycol (MW 4000) 1.1 1.7 2.0 Misc. (water) 6.2 4.3 5.0 100.0 100.0 100.0
- the base granule is prepared by a conventional spray drying process in which the starting ingredients are formed into a slurry and passed though a spray drying tower having a counter current stream of hot air (200-300°C) resulting in the formation of porous granules.
- the admixed agglomerates are formed from two feed streams of various starting detergent ingredients which are continuously fed, at a rate of 1400 kg/hr, into a Schugi high shear granulator (1000-4000 RPM) or a Lödige CB-30 mixer/densifier, one of which comprises a liquid binder containing either: I ) PVNO and water or 2) a copolymer of epichlorohydrin and a cyclic amine moiety (IME) and water or 3) the IME material, alkyl ethoxy sulfate surfactant paste and water; and the other stream containing starting dry detergent containing a premixed mixture of either: 1) an ester modified carboxy methyl cellulose, aluminosilicate and sodium carbonate or 2) ester modified carboxy methyl cellulose and aluminosilicate.
- a Schugi high shear granulator 1000-4000 RPM
- Lödige CB-30 mixer/densifier one of which comprises a liquid
- the rotational speed of the shaft in the Lödige CB-30 mixer/densifier is about 1400 rpm and the median residence time is about 5-10 seconds.
- the contents from the Lödige CB-30 mixer/densifier are continuously fed into a Lödige KM-600 mixer/densifier for further agglomeration during which the mean residence time is about 1-2 minutes.
- the resulting detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed cooler before being admixed with the spray dried granules.
- These agglomerates are then admixed with agglomerates made with a surfactant paste that contains surfactant and water and dry detergent ingredients containing dry detergent material containing aluminosilicate and sodium carbonate.
- adjunct detergent ingredients are sprayed on or dry added to the blend of agglomerates and granules.
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Claims (10)
- Verfahren zur kontinuierlichen Herstellung von Detergensagglomeraten. gekennzeichnet durch die Schritte:(A) kontinuierliches Mischen eines flüssigen Bindemittels und trockener Detergensmaterialien in einem Hochgeschwindigkeitsmischer/Verdichter, um Detergensagglomerate zu erhalten, wobei das Verhältnis des flüssigen Bindemittels zu dem trockenen Detergensmaterial 1:10 bis 10:1 beträgt, wobei die trockenen Detergensmaterialien modifizierte Carboxymethylcellulose umfassen:(B) wahlweise Mischen der Detergensagglomerate in einem Mäßiggeschwindigkeitsmischer/Verdichter, um die Detergensagglomerate weiter zu verdichten und zu agglomerieren; und(C) Trocknen der Detergensagglomerate, um so deren Dichte zu erhöhen.
- Verfahren zur Herstellung einer hochdichten Detergenszusammensetzung, gekennzeichnet durch die Schritte:(A) kontinuierliches Mischen eines flüssigen Bindemittels und trockener Detergensmaterialien in einem Hochgeschwindigkeitsmischer/Verdichter, um erste Detergensagglomerate zu erhalten, wobei das Verhältnis des flüssigen Bindemittels zu dem trockenen Detergensmaterial 1:10 bis 10:1 beträgt, wobei die trockenen Detergensmaterialien modifizierte Carboxymethylcellulose umfassen;(B) wahlweise Mischen der ersten Detergensagglomerate in einem Mäßiggeschwindigkeitsmischer/Verdichter, um deren Dichte zu erhöhen;(C) Trocknen der ersten Detergensagglomerate, um deren Dichte weiter zu erhöhen;(D) kontinuierliches Mischen einer Detergenstensidpaste und zusätzlicher trockener Detergensmaterialien in einem Hochgeschwindigkeitsmischer/Verdichter, um zweite Detergensagglomerate zu erhalten, wobei das Verhältnis der Tensidpaste zu dem zusätzlichen, trockenen Detergensmaterial 1:10 bis 10:1 beträgt;(E) Mischen der zweiten Detergensagglomerate in einem Mäßiggeschwindigkeitsmischer/Verdichter, um deren Dichte zu erhöhen;(F) Trocknen der zweiten Detergensagglomerate, um deren Dichte weiter zu erhöhen; und(G) Mischen der ersten Detergensagglomerate und der zweiten Detergentsagglomerate, um die hochdichte Detergenszusammensetzung zu bilden.
- Verfahren nach irgendeinem der Ansprüche 1-2, wobei das flüssige Bindemittel gekennzeichnet ist durch Wasser, Tensidpaste, gewählt aus verzweigten und linearen anionischen, nichtionischen, zwitterionischen, ampholytischen und kationischen Klassen und kompatiblen Mischungen hiervon, und ein Polymer, gewählt aus der Gruppe, bestehend aus Farbstoffübertragungsmitteln, Polyaminen, Homopolymeren und Copolymeren aus Polyacrylaten, Homopoylmeren und Copolymeren aus Polyacrylamiden, Homopolymeren und Copolymeren aus Polyvenylalkohol. Homopolymeren und Copolymeren aus Polyvenylpyrrolidon, Polymaleaten, aliphatischen Polyestern, natürlichen Proteinen, synthetischen nichtkristallinen Polyaminosäuren, wasserlöslichen Nylons, Polyethylenglykol, Polyacrylat und Mischungen hiervon.
- Verfahren nach mindestens einem der Ansprüche 1-3, wobei das flüssige Bindemittel gekennzeichnet ist durch (1) eine Mischung aus Tensid, gewählt aus der Gruppe LAS, Natriumethoxysulfat und Mischungen hiervon; und (2) ein Polymer, gewählt aus der Gruppe, bestehend aus einem Polyvinyl-N-Oxid, einem Copolymer aus Epichlorhydrin und einer zyklischen Amingruppe, Homopolymeren und Copolymeren von Polyacrylaten und Mischungen hiervon.
- Verfahren nach mindestens einem der Ansprüche 1-4, wobei die Tensidpaste eine Viskosität, gemessen bei 70°C und bei Scherraten von 10 bis 100 s-1, von 50.000 cps bis 450.000 cps besitzt, und weiterhin gekennzeichnet ist durch Wasser und Zusatztensid, gewählt aus der Gruppe, bestehend aus nichtionischen, zwitterionischen, ampholytischen und kationischen Tensiden und Mischungen hiervon.
- Verfahren zur kontinuierlichen Herstellung einer hochdichten Detergenszusammensetzung, gekennzeichnet durch die Schritte:(A) Sprühtrocknen einer Zusatzdetergensbestandeile enthaltenden, wässrigen Aufschlämmung, um sprühgetrocknete Granulate zu bilden;(B) kontinuierliches Mischen eines flüssigen Bindemittels und trockener Detergensmaterialien in einem Hochgeschwindigkeitsmischer/Verdichter, um Detergensagglomerate zu erhalten, wobei das Verhältnis des flüssigen Bindemittels zu den trockenen Detergensmaterialien 1:10 bis 10:1 beträgt, wobei die trockenen Detergensmaterialien modifizierte Carboxymethylcellulose umfassen;(C) wahlweise Mischen der Detergensagglomerate in einem Mäßiggeschwindigkeitsmlscher/Verdichter, um deren Dichte zu erhöhen;(D) Trocknen der Detergensagglomerate, um deren Dichte weiter zu erhöhen; und(E) Mischen der Granulate und der Detergensagglomerate miteinander, um die hochdichte Detergenszusammensetzung zu bilden.
- Verfahren zur kontinuierlichen Herstellung einer hochdichten Detergenszusammensetzung, gekennzeichnet durch die Schritte:(A) kontinuierliches Mischen eines flüssigen Bindemittels und trockener Detergensmateriallen in einem Hochgeschwindigkeitsmischer/Verdichter, um erste Detergensagglomerate zu erhalten, wobei das Verhältnis des flüssigen Bindemittels zu dem trockenen Detergensmaterial 1:10 bis 10:1 beträgt, wobei die trockenen Detergensmaterialien modifizierte Carboxymethylcellulose umfassen;(B) wahlweise Mischen der ersten Detergensagglomerate in einem Mäßiggeschwindigkeitsmischer/Verdichter, um deren Dichte zu erhöhen;(C) Trocknen der ersten Detergensagglomerate, um deren Dichte weiter zu erhöhen;(D) kontinuierliches Mischen eines Säurevorläufers eines anionischen Tensids und zusätzlicher trockener Detergensmaterialien, die ein alkalisches anorganisches Material enthalten, das in der Lage ist, den Säurevorläufer zu neutralisieren, in einem Hochgeschwindigkeitsmischer/Verdichter, um zweite Detergensagglomerate zu erhalten, wobei das Verhältnis des anionischen Tensids zu den zusätzlichen trockenen Detergensmaterialien 1:10 bis 10:1 beträgt;(E) wahlweise Mischen der zweiten Detergensagglomerate in einem Mäßiggeschwindigkeitsmischer/Verdichter, um deren Dichte zu erhöhen;(F) Trocknen der zweiten Detergensagglomerate, um deren Dichte zu erhöhen; und Mischen der ersten Detergensagglomerate und der zweiten Detergensagglomerate, um die hochdichte Detergenszusammensetzung zu bilden.
- Verfahren zur kontinuierlichen Herstellung von Detergensagglomeraten, gekennzeichnet durch die Schritte:(A) kontinuierliches Mischen eines flüssigen Bindemittels und trockener Detergensmaterialien in einem Hochgeschwindigkeitsmischer/Verdichter, um Detergensagglomerate zu erhalten, wobei das Verhältnis des flüssigen Bindemittels zu dem trockenen Detergensmaterial 1:10 bis 10:1 beträgt, wobei die trockenen Detergensmaterialien im Wesentlichen aus modifizierter Carboxymethylcellulose bestehen;(B) wahlweise Mischen der Detergensagglomerate in einem Mäßiggeschwindigkeitsmischer/Verdichter, um die Detergensagglomerate weiter zu verdichten und zu agglomerieren; und(C) Trocknen der Detergensagglomerate, um deren Dichte zu erhöhen.
- Verfahren nach mindestens einem der Ansprüche 1-8, wobei das flüssige Bindemittel gekennzeichnet ist durch Wasser, Tensidpaste, gewählt aus verzweigten und linearen anionischen, nichtionischen, zwitterionischen, ampholytischen und kationischen Klassen und kompatiblen Mischungen hiervon, und ein Polymer, gewählt aus der Gruppe, bestehend aus Farbstoffübertragungsmitteln, Polyaminen. Homopolymeren und Copolymeren aus Polyacrylaten, Homopoylmeren und Copolymeren aus Polyacrylamiden, Homopolymeren und Copolymeren aus Polyvenylalkohol, Homopolymeren und Copolymeren aus Polyvenylpyrrolidon, Polymaleaten, aliphatischen Polyestern, natürlichen Proteinen, synthetischen nichtkristallinen Polyaminosäuren, wasserlöslichen Nylons, Polyethylenglykol, Polyacrylat und Mischungen hiervon.
- Verfahren nach mindestens einem der Ansprüche 1-9, wobei das flüssige Bindemittel gekennzeichnet ist durch (1) eine Mischung aus Tensid, gewählt aus der Gruppe LAS, Natriumethoxysulfat und Mischungen hiervon; und (2) ein Polymer, gewählt aus der Gruppe, bestehend aus einem Polyvinyl-N-Oxid, einem Copolymer aus Epichlorhydrin und einer zyklischen Amingruppe, Homopolymeren und Copolymeren von Polyacrylaten und Mischungen hiervon.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US11330698P | 1998-12-22 | 1998-12-22 | |
US113306P | 1998-12-22 | ||
PCT/US1999/030556 WO2000037598A1 (en) | 1998-12-22 | 1999-12-21 | Processes for making a granular detergent composition containing modified carboxy methyl cellulose |
Publications (2)
Publication Number | Publication Date |
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EP1141197A1 EP1141197A1 (de) | 2001-10-10 |
EP1141197B1 true EP1141197B1 (de) | 2002-11-27 |
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Application Number | Title | Priority Date | Filing Date |
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EP99966543A Expired - Lifetime EP1141197B1 (de) | 1998-12-22 | 1999-12-21 | Verfahren zur herstellung eines granularen waschmittels enthaltend eine modifizierte carboxymethylcellulose |
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EP (1) | EP1141197B1 (de) |
JP (1) | JP2002533530A (de) |
CN (1) | CN1168809C (de) |
AR (1) | AR023072A1 (de) |
AT (1) | ATE228559T1 (de) |
AU (1) | AU2205500A (de) |
BR (1) | BR9916501A (de) |
CA (1) | CA2352814A1 (de) |
DE (1) | DE69904236T2 (de) |
ES (1) | ES2186431T3 (de) |
WO (1) | WO2000037598A1 (de) |
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WO2001059054A1 (en) * | 2000-02-10 | 2001-08-16 | The Procter & Gamble Company | Laundry detergent compositions with a combination of a cyclic amine polymer and a dye transfer inhibitor |
US20050187130A1 (en) * | 2004-02-23 | 2005-08-25 | Brooker Alan T. | Granular laundry detergent composition comprising an anionic detersive surfactant, and low levels of, or no, zeolite builders and phosphate builders |
DE102004020010A1 (de) * | 2004-04-21 | 2005-11-17 | Henkel Kgaa | Verfahren zur Herstellung von Polymer-Granulaten |
US9376648B2 (en) | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
CN108362166A (zh) * | 2018-01-10 | 2018-08-03 | 马斌祥 | 一种空分主板式换热器内部油污清洗方法 |
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JPS596293A (ja) * | 1982-07-05 | 1984-01-13 | ライオン株式会社 | 粒状洗剤用添加剤 |
US4441881A (en) * | 1982-09-07 | 1984-04-10 | Lever Brothers Company | Detergent compositions containing ethoxylated fatty alcohols with narrow ethylene oxide distributions |
JP4267075B2 (ja) * | 1996-12-26 | 2009-05-27 | ザ、プロクター、エンド、ギャンブル、カンパニー | 外観および完全性の利益をそれで洗濯された布帛に与えるためにセルロース系重合体を有する洗濯洗剤組成物 |
CA2303083C (en) * | 1997-09-15 | 2007-04-10 | The Procter & Gamble Company | Laundry detergent compositions with anionically modified, cyclic amine based polymers |
-
1999
- 1999-12-21 AU AU22055/00A patent/AU2205500A/en not_active Abandoned
- 1999-12-21 JP JP2000589655A patent/JP2002533530A/ja not_active Withdrawn
- 1999-12-21 ES ES99966543T patent/ES2186431T3/es not_active Expired - Lifetime
- 1999-12-21 CA CA002352814A patent/CA2352814A1/en not_active Abandoned
- 1999-12-21 BR BR9916501-5A patent/BR9916501A/pt not_active Application Discontinuation
- 1999-12-21 EP EP99966543A patent/EP1141197B1/de not_active Expired - Lifetime
- 1999-12-21 AT AT99966543T patent/ATE228559T1/de not_active IP Right Cessation
- 1999-12-21 WO PCT/US1999/030556 patent/WO2000037598A1/en active IP Right Grant
- 1999-12-21 DE DE69904236T patent/DE69904236T2/de not_active Expired - Fee Related
- 1999-12-21 CN CNB998150185A patent/CN1168809C/zh not_active Expired - Fee Related
- 1999-12-22 AR ARP990106661A patent/AR023072A1/es unknown
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ES2186431T3 (es) | 2003-05-01 |
AU2205500A (en) | 2000-07-12 |
DE69904236T2 (de) | 2003-08-21 |
CA2352814A1 (en) | 2000-06-29 |
BR9916501A (pt) | 2001-09-04 |
WO2000037598A1 (en) | 2000-06-29 |
ATE228559T1 (de) | 2002-12-15 |
CN1168809C (zh) | 2004-09-29 |
CN1331738A (zh) | 2002-01-16 |
DE69904236D1 (de) | 2003-01-09 |
EP1141197A1 (de) | 2001-10-10 |
AR023072A1 (es) | 2002-09-04 |
JP2002533530A (ja) | 2002-10-08 |
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