EP1141197A1 - Procedes permettant de preparer une composition detergente en granules contenant de la carboxymethylcellulose modifiee - Google Patents
Procedes permettant de preparer une composition detergente en granules contenant de la carboxymethylcellulose modifieeInfo
- Publication number
- EP1141197A1 EP1141197A1 EP99966543A EP99966543A EP1141197A1 EP 1141197 A1 EP1141197 A1 EP 1141197A1 EP 99966543 A EP99966543 A EP 99966543A EP 99966543 A EP99966543 A EP 99966543A EP 1141197 A1 EP1141197 A1 EP 1141197A1
- 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.)
- Granted
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 221
- 239000000203 mixture Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 81
- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 35
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 35
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 35
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 35
- 229940105329 carboxymethylcellulose Drugs 0.000 title claims abstract description 35
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 73
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000004094 surface-active agent Substances 0.000 claims abstract description 47
- 239000011230 binding agent Substances 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000008187 granular material Substances 0.000 claims description 47
- 239000004615 ingredient Substances 0.000 claims description 32
- 239000011734 sodium Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 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 18
- 229920001519 homopolymer Polymers 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000003945 anionic surfactant Substances 0.000 claims description 15
- 229920000058 polyacrylate Polymers 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001694 spray drying Methods 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 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 125000002091 cationic group Chemical group 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
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 229920001778 nylon 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
- 239000002563 ionic surfactant Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- -1 alkyl alkoxy sulfates Chemical class 0.000 description 28
- 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
- 238000005054 agglomeration Methods 0.000 description 17
- 230000002776 aggregation Effects 0.000 description 17
- 239000004744 fabric Substances 0.000 description 16
- 239000012530 fluid Substances 0.000 description 16
- 238000005342 ion exchange Methods 0.000 description 15
- 229910052770 Uranium Inorganic materials 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 239000002736 nonionic surfactant Substances 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 150000008051 alkyl sulfates Chemical class 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
- 150000004665 fatty acids Chemical class 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
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 150000004760 silicates Chemical class 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 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
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 235000019864 coconut oil Nutrition 0.000 description 4
- 239000003240 coconut oil Substances 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 238000008947 Amm Methods 0.000 description 2
- 238000006677 Appel reaction Methods 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
- 150000001298 alcohols Chemical class 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
- 238000010923 batch production Methods 0.000 description 2
- 239000007844 bleaching agent Substances 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
- 238000001816 cooling Methods 0.000 description 2
- 230000002939 deleterious effect Effects 0.000 description 2
- 125000004185 ester group Chemical group 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 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
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 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
- 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
- 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
- 150000007513 acids Chemical class 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
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005192 alkyl ethylene group Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 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
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 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
- 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
- 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
- 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
- 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
- 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
- 239000012188 paraffin wax Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920005646 polycarboxylate 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
- 229910052702 rhenium Inorganic materials 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
- 238000003860 storage Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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 charactenstics 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 m a spray-drymg 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 m 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 m 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. Improved cleaning performance above and beyond current standards, especially for granular detergent compositions to be used under colder wash water conditions and/or in hard water, has been difficult to attain Therefore, it would be desirable to have a process for making a detergent composition which exhibits improved cleaning performance over a wide variety of soils and stams.
- 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 about 1 : 10 to about 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 densify 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, polyammes, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrohdone, polymaleates, aliphatic polyesters, natural proteins, synthetic non- crystallme polyammoacids, 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 epichlorohydrm and a cyclic amine moiety, and mixtures thereof
- a preferred aspect of the invention includes the use of a surfactant paste m 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 m which the average number of carbon atoms in the alkyl group is from about 1 1 to 13, abbreviated as Ci 1.13 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 about 1 T 0 to about 10 1, (B) optionally mixing the second detergent agglomerates m 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 m 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 m the washing machine and on the fabrics.
- the inventors also found that 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 dispersabihty 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 j .13
- 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 epichlorohyd ⁇ n and a cyclic amine moiety or polyvinyl N- Oxide, and mixtures thereof m combination with dry detergent materials that include a modified carboxy methyl cellulose.
- 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-drymg 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 is preferably included m the detergent composition.
- the resulting detergent compositions preferably comprises from about 0.01% to about 4%, more preferably from about 0.05% to about 2%, and most preferably from about 0.1% to about 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, b ⁇ ghteners, perfumes, hydrotropes, dyes, pigments, polymeric dispersing agents, pH controlling agents, chelants, 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 m 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:
- each R is selected from the group consisting of 2, Re, and
- each R2 is independently selected from the group consisting of H and C1 -C4 alkyl; O
- each R4 is independently selected from the group consisting of H, CJ-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylammoalkyl, dialkylammoalkyl, prpe ⁇ dinoalkyl, morphohnoalkyl, cycloalkylammoalkyl and hydroxyalkyl; each R5 is independently selected from the group consisting of H, C1 -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R 4 ) 2 N-alkyl, and (R 4 ) 3 N-alkyl.
- M is a suitable cation selected from the group consisting of Na, K, l/2Ca, and l/2Mg; each x is from 0 to about 5, each y is from about 1 to about 5; and provided that: the Degree of Substitution for group R H is between about 0.001 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05; the Degree of Substitution for group Re wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0 3 and 1.0, and most preferably between about 0.4 and 0.7; if any R H bears a positive charge, it is balanced by a suitable amon; and two R4's on the same nitrogen can together form a ring structure selected from the group consisting of pipe ⁇ dme and morpholme.
- 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 co-pending applications entitled "Laundry Detergent Compositions With Cellulosic Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith", PCT Ser No. PCT/US98/19139 and PCT Ser. No. PCT/US98/19142. Both of these applications were filed in the PCT on September 15, 1998, in the name of Jennifer A. Leupin et al , and they claim the benefit of U.S. provisional application 60/058,892, filed on September 15, 1997 The entire disclosures of PCT Ser. No.
- PCT/US98/19139 and PCT Ser. No. PCT/US98/19142 are incorporated herein by reference
- 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 aluminosihcates, 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 aluminosihcate ion exchange materials and sodium carbonate.
- the aluminosihcate 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 aluminosihcate ion exchange material is produced.
- the aluminosihcate ion exchange materials used herein are preferably produced m accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
- the aluminosihcate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosihcate do not exhibit as high of an exchange rate and capacity as provided by the sodium form.
- the aluminosihcate ion exchange material preferably is m over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
- the aluminosihcate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
- particle size diameter represents the average particle size diameter of a given aluminosihcate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope
- the preferred particle size diameter of the aluminosihcate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
- the aluminosihcate ion exchange material has the formula Na z [(A10 2 ) z .(S ⁇ 0 2 ) y ]xH 2 0 wherein z and y are integers of at least 6. the molar ratio of z to y is from about 1 to about 5 and x is from about 10 to about 264. More preferably, the aluminosihcate has the formula
- These preferred aluminosilicates are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
- Naturally-occurring or synthetically derived aluminosihcate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669, the disclosure of which is incorporated herein by reference.
- the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaC ⁇ 3 hardness/gram, calculated on an anhydrous basis, and which is preferably m a range from about 300 to 352 mg equivalent of CaQ hardness/gram. Additionally, the instant aluminosihcate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/m ⁇ nute/-gram/gallon, and more preferably in a range from about 2 grains Ca ++ /gallon/m ⁇ nute/-gram/gallon to about 6 grains Ca ++ /gallon/mmute/-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, polyammes, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrohdone, polymaleates, aliphatic polyesters, natural proteins, synthetic non-crystallme polyammoacids, water soluble nylons, polyethylene glycol, polyacrylate and mixtures thereof.
- Detergent compositions made with the agglomerates of this invention preferably comprise from about 0.01% to about 4%, more preferably from about 0.05% to about 2%, and most preferably from about 0.1% to about 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 about 11 to 13 (abbreviated as Ci ⁇ . ⁇ 3 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-v ⁇ nylpy ⁇ dme-N- oxide) "PVNO".
- Copolymers of N-vmylpyrrohdone and N-vmyhmidazole 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. The entire disclosure of U.S. Patent No. 5,804,543 is incorporated herein by reference.
- preferred liquid binders for use m this invention are polyammes, and even more preferred are copolymers of epichlorohyd ⁇ n and a cyclic amine moiety. Descriptions and example of the preferred polyammes for use in this invention can be found in the following PCT Patent Applications: PCT/US98/19143.
- PCT/US98/19141, and PCT/US98/19144 all three of these applications were filed internationally on September 15, 1998 and they all claim the benefit of U.S Provisional Application No. 60/058,931, which was filed on September 15, 1997.
- PCT US98/19141, and PCT/US98/19144 are incorporated herein by reference.
- U.S. Provisional Application No. 60/103,978 which was filed on October 13, 1998. discloses a detergent composition comprising copolymers of epichlorohydrm and a cyclic amine moiety with modified carboxy methyl cellulose materials.
- the entire disclosure of U.S. Provisional Application No. 60/103,978 is incorporated herein by reference.
- the process comprises the step of spraying an additional binder m 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 pyrrohdone 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 disclosure of which is incorporated herein by reference.
- 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 vanes 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.
- the viscoelastic surfactant paste used in the process has a consistency K at 70°C of from about 50,000 to about 450,000 cPoise sec" " 1 (500 to 2,500 Poise-sec”” 1 ), more preferably from about 100,000 to about 195,000 cPoise-sec” " 1 (1 ,000 to 1,950 Poise-sec”” 1 ), and most preferably from about 120,000 to about 180,000 cPoise-sec" "1 (1,200 to 1,800 Poise-sec” " 1 ).
- the surfactant paste has a shear index n of from about 0.05 to about 0.25, more preferably from about 0.08 to about 0.20 and most preferably from about 0.10 to about 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, Laughhn et al., issued December 30, 1975, both of which are incorporated herein by reference.
- 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, both of which are also incorporated herein by reference.
- detergent surfactants useful m 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 sulfu ⁇ c reaction products having m their molecular structure a straight-chain alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfu ⁇ c acid ester group.
- alkyl is the alkyl portion of acyl groups.
- these group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfatmg the higher alcohols (C Intel 1 _ carbon atoms) such as those produced by reducing the glyce ⁇ des of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates m which the alkyl group contains from about 9 to about 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 about 11 to 13, abbreviated as C 1 1.13 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 monoglyce ⁇ de sulfonates and sulfates; sodium or potassium of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms
- suitable anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane- 1 -sulfomc acids containing from about 2 to 9 carbon
- Preferred adjunct anionic surfactants are C.tician . send linear alkylbenzene sulfonate and C, Proceedings . disturbing 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. » 1 answering 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 about 20% to about 40% of a mixture of sodium C.tician 1 _ linear alkylbenzene sulfonate and sodium C. provoke .
- alkyl sulfate m a weight ratio of about 2: 1 to 1 :2.
- Another preferred embodiment of the detergent composition includes a mixture of Ci Q_ ⁇ g alkyl sulfate and C1 Q- 18 alkyl ethoxy sulfate m a weight ratio of about 80:20.
- Nonionic surfactants are also useful in the instant invention.
- Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophihc 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 hydrophihc 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 about 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from about 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
- An additional group of nonionics suitable for use herein are semi-polar nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from abut
- Preferred nonionic surfactants are of the formula R (OC,H .) OH, wherein R is a 2 4 y n C, -C, alkyl group or a C n -C. » alkyl phenyl group, and n is from 3 to about 80.
- Particularly preferred are condensation products of C. ⁇ -C, - alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e g., C. ⁇ -C. , 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, the disclosures of which are incorporated herein by reference.
- Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocychc secondary and tertiary ammes in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubihzmg group
- Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphomum, and sulfomum compounds in which one of the aliphatic substituents contains from about 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 ammes can have characteristics similar to catiomc 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, incorporated herein by reference.
- Cationic surfactants are often used m 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 m U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3. 1976, the disclosure of which is incorporated herein by reference.
- 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 documents are incorporated herein by reference. 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 asurfactant 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 about 10% to about 50%, preferably from about 15% to about 45% and, most preferably from about 20% to about 40% of an aluminosihcate or zeolite builder and from about 10% to about 40%, preferably from about 15% to about 30% and, most preferably from about 15% to about
- the dry starting detergent material comprises from about 10% to about 50%, preferably from about 15% to about 45% and, most preferably from about 20% to about 40% of an aluminosihcate or zeolite builder and from about 10% to about 40%, preferably from about 15% to about 30% and, most preferably from about 15% to about 25% of an ester modified carboxy methyl cellulose.
- 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 about 1 : 10 to about 10 1, more preferably from about 1 -4 to about 4:1 and, most preferably from about 2: 1 to about 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 Lbdige CB mixer or similar brand mixer.
- a high speed mixer/densifier which preferably is a Lbdige 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 about 300 rpm to about 2500 rpm, more preferably from about 400 rpm to about 1600 rpm
- the mean residence time of the detergent ingredients in the high speed mixer/densifier is preferably m range from about 2 seconds to about 45 seconds, and most preferably from about 5 seconds to about 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 Lodige KM (Ploughshare) mixer, Drais® K-T 160 mixer or similar brand mixer.
- the mam centrally rotating shaft speed is from about 30 to about 160 rpm, more preferably from about 50 to about 100 rpm.
- the mean residence time in the moderate speed mixer/densifier is preferably from about 0.25 minutes to about 15 minutes, most preferably the residence time is about 0.5 to about 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.
- the instant process imparts from about 5 x lO 1 ⁇ erg/kg to about 2 x lO ⁇ erg/kg at a rate of from about 3 x 10° erg/kg-sec to about 3 x l ⁇ " 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 withm the scope of the skilled artisan
- the density of the resulting detergent agglomerates exiting the fluid bed dryer is at least 400 g/1, more preferably from about 500 g/1 to about 600 g/1
- the particle porosity of the resulting detergent agglomerates of the composition is preferably in a range from about 5% to about 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 about 400 microns to about 700 microns, and more preferably from about 475 microns to about 600 microns
- the phrase "median particle size" refers to individual agglomerates and not individual particles or detergent granules
- the combination of the above-referenced porosity and particle size results in agglomerates mg density values of 600 g/1 and higher Such a feature is especially useful in the production of low dosage laundry detergents as well as other granular compositions such as dishwashing compositions
- 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 (1) 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 It should be understood that the coating agent can be added in any one or a combination of streams, see Capeci et al, U S Patent
- 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 and the like
- 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 m 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, b ⁇ ghteners and enzymes onto the finished agglomerates to provide a more complete detergent composition.
- Such techniques and ingredients are well known in the art.
- Spray Drying Process One or more spray drying techniques can be used alone, or in combination with the aforementioned agglomeration processes, to make detergent compositions m accordance with the instant invention.
- One or more spray-drymg towers may be employed to manufacture granular laundry detergents which often have a density of about 500 g/1 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-drymg tower, using conventional techniques, at temperatures of about 175°C to about 225°C
- additional process steps as described herein can be optionally used to obtain the level of density (i.e., > 650 g/1) required by modern compact, low dosage detergent products.
- spray-d ⁇ ed 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 "Lodige CB 30" or “Lodige 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 "Lodige KM" (Series 300 or 600) or “Lodige 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. Lodige KM
- 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 m 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-d ⁇ ed granules in the process of the invention.
- Admixing Process includes 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 m 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 m 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 m 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. Lodige KM) for further agglomeration resulting in the finished high density detergent composition.
- a moderate speed mixer/densifier e.g. Lodige KM
- the surfactant paste is premixed or extruded m a mixing or extruding apparatus such as a twm-screw extruder (e.g., Werner and Pfleiderer, Contmua Series) to structure the paste for easier agglomeration.
- a mixing or extruding apparatus such as a twm-screw extruder (e.g., Werner and Pfleiderer, Contmua Series) to structure the paste for easier agglomeration.
- structuring agents such as polymers, sodium hydroxide, sodium chloride, postassium hydroxide sihcates and the like 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, b ⁇ ghteners and the like 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 Lodige 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, aluminosihcate and sodium carbonate.
- the rotational speed of the shaft in the Lodige CB-30 mixer/densifier is about 1400 rpm and the mean residence time is about 10 seconds.
- the contents from the Lodige CB-30 mixer/densifer are continuously fed into a Lodige 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, aluminosihcate is fed after the Lodige 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.
- Table I The composition of the detergent agglomerate mixture exiting the fluid bed cooler for three process runs are set forth in Table I below:
- Polyethylene glycol (MW 4000) 1.1 1.7 2.0
- EXAMPLE II-V Several detergent compositions made in accordance with the invention and specifically for top-loading washing machines are exemplified below.
- 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 Lodige CB-30 mixer/densifier, one of which comprises a liquid binder containing either: 1) PVNO and water or 2) a coploymer of epichlorohyd ⁇ n and a cyclic amme 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, aluminosihcate and sodium carbonate or 2) ester modified carboxy methyl cellulose and aluminosihcate.
- a Schugi high shear granulator 1000-4000 RPM
- a Lodige CB-30 mixer/densifier one of which comprises
- the rotational speed of the shaft in the Lodige CB-30 mixer/densifier is about 1400 rpm and the median residence time is about 5-10 seconds.
- the contents from the Lodige CB-30 mixer/densifier are continuously fed into a Lodige 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 aluminosihcate and sodium carbonate.
- the remaining adjunct detergent ingredients are sprayed on or dry added to the blend of agglomerates and granules.
- PolyethyleneGlycol (MW 4000) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
- Ci 2_i3 linear alkylbenzene sulfonate Na 6.0 6.0 6.0 6.0
- Admix c 12-15 alk y J ethoxylate (EO 7) 2.0 2.0 2.0 2.0 Perfume 0.3 0.3 0.3 0.3 0.3
- Termamyl amylase 60 KNU/g ⁇ 0.3 0.3 0.3 0.3 0.3
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Glanulating (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11330698P | 1998-12-22 | 1998-12-22 | |
US113306P | 1998-12-22 | ||
PCT/US1999/030556 WO2000037598A1 (fr) | 1998-12-22 | 1999-12-21 | Procedes permettant de preparer une composition detergente en granules contenant de la carboxymethylcellulose modifiee |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1141197A1 true EP1141197A1 (fr) | 2001-10-10 |
EP1141197B1 EP1141197B1 (fr) | 2002-11-27 |
Family
ID=22348705
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99966543A Expired - Lifetime EP1141197B1 (fr) | 1998-12-22 | 1999-12-21 | Procedes permettant de preparer une composition detergente en granules contenant de la carboxymethylcellulose modifiee |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP1141197B1 (fr) |
JP (1) | JP2002533530A (fr) |
CN (1) | CN1168809C (fr) |
AR (1) | AR023072A1 (fr) |
AT (1) | ATE228559T1 (fr) |
AU (1) | AU2205500A (fr) |
BR (1) | BR9916501A (fr) |
CA (1) | CA2352814A1 (fr) |
DE (1) | DE69904236T2 (fr) |
ES (1) | ES2186431T3 (fr) |
WO (1) | WO2000037598A1 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001059054A1 (fr) * | 2000-02-10 | 2001-08-16 | The Procter & Gamble Company | Compositions de detergents a lessive possedant une combinaison d'un polymere d'amine cyclique et d'un inhibiteur de transfert de couleurs |
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 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN1213137C (zh) * | 1996-12-26 | 2005-08-03 | 普罗格特-甘布尔公司 | 含有对所洗涤的织物的外观和整体有利的纤维素类聚合物的洗衣洗涤剂组合物 |
JP2001516797A (ja) * | 1997-09-15 | 2001-10-02 | ザ、プロクター、エンド、ギャンブル、カンパニー | 陰イオン的に改変された環状アミン系ポリマーを有する洗濯用洗剤組成物 |
-
1999
- 1999-12-21 DE DE69904236T patent/DE69904236T2/de not_active Expired - Fee Related
- 1999-12-21 WO PCT/US1999/030556 patent/WO2000037598A1/fr active IP Right Grant
- 1999-12-21 ES ES99966543T patent/ES2186431T3/es not_active Expired - Lifetime
- 1999-12-21 CA CA002352814A patent/CA2352814A1/fr not_active Abandoned
- 1999-12-21 AT AT99966543T patent/ATE228559T1/de not_active IP Right Cessation
- 1999-12-21 EP EP99966543A patent/EP1141197B1/fr not_active Expired - Lifetime
- 1999-12-21 JP JP2000589655A patent/JP2002533530A/ja not_active Withdrawn
- 1999-12-21 CN CNB998150185A patent/CN1168809C/zh not_active Expired - Fee Related
- 1999-12-21 AU AU22055/00A patent/AU2205500A/en not_active Abandoned
- 1999-12-21 BR BR9916501-5A patent/BR9916501A/pt not_active Application Discontinuation
- 1999-12-22 AR ARP990106661A patent/AR023072A1/es unknown
Non-Patent Citations (1)
Title |
---|
See references of WO0037598A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN1168809C (zh) | 2004-09-29 |
ES2186431T3 (es) | 2003-05-01 |
WO2000037598A1 (fr) | 2000-06-29 |
EP1141197B1 (fr) | 2002-11-27 |
DE69904236T2 (de) | 2003-08-21 |
BR9916501A (pt) | 2001-09-04 |
CN1331738A (zh) | 2002-01-16 |
AU2205500A (en) | 2000-07-12 |
CA2352814A1 (fr) | 2000-06-29 |
DE69904236D1 (de) | 2003-01-09 |
ATE228559T1 (de) | 2002-12-15 |
JP2002533530A (ja) | 2002-10-08 |
AR023072A1 (es) | 2002-09-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2199370C (fr) | Procede de production d'une composition detergente a haute densite comprenant certains flux de recyclage | |
EP0782612B1 (fr) | Procede d'elaboration d'une composition detergente a haute densite dans un melangeur/densificateur unique avec certains flux de recyclage | |
CA2138125C (fr) | Procede pour la fabrication de compositions concentrees de detergents | |
EP1124937B1 (fr) | Procedes de preparation d'une composition detergente granuleuse avec une apparence et une solubilite ameliorees | |
MXPA97002099A (en) | Procedure to make a high density detergent composition that includes recirculation currents select | |
CA2028204A1 (fr) | Compositions detergentes | |
EP0777724A1 (fr) | Procede d'agglomeration pour fabriquer un detergent, utilisant des tours de sechage par pulverisation | |
CA2171528C (fr) | Compositions detergentes granulaires comprenant un agent tensio-actif non ionique | |
US5565137A (en) | Process for making a high density detergent composition from starting detergent ingredients | |
IE930521A1 (en) | Process and compositions for compact detergents | |
EP1141197B1 (fr) | Procedes permettant de preparer une composition detergente en granules contenant de la carboxymethylcellulose modifiee | |
CA2305324C (fr) | Procede de production d'une composition detergente granulaire contenant des tensioactifs ramifies en milieu de chaine | |
US6589931B2 (en) | Granular detergent composition having an improved solubility | |
WO1995010595A1 (fr) | Procede continu pour produire un detergent granulaire a haute densite | |
EP1299511B1 (fr) | Composition de detergent granulaire a solubilite accrue | |
AU731828B2 (en) | Process for preparing high bulk density detergent compositions | |
MXPA01006521A (en) | Processes for making a granular detergent composition containing modified carboxy methyl cellulose | |
MXPA01004184A (en) | Processes for making granular detergent composition having improved appearance and solubility |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20010627 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: SHERRINGTON, PAUL, RICHARD Inventor name: LEUPIN, JENNIFER, ANN Inventor name: TATSUNO, TERUAKI Inventor name: JONES, RICCI, JOHN |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
17Q | First examination report despatched |
Effective date: 20011218 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20021127 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20021127 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20021127 Ref country code: CH Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20021127 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20021127 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20021127 |
|
REF | Corresponds to: |
Ref document number: 228559 Country of ref document: AT Date of ref document: 20021215 Kind code of ref document: T |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021221 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021223 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20021231 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 69904236 Country of ref document: DE Date of ref document: 20030109 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030227 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030227 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20030227 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2186431 Country of ref document: ES Kind code of ref document: T3 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20021127 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
ET | Fr: translation filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030701 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20031110 Year of fee payment: 5 |
|
26N | No opposition filed |
Effective date: 20030828 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20031215 Year of fee payment: 5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041222 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050701 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20050701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20051221 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20051230 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20041222 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20061201 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070703 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20081020 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20071231 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20101123 Year of fee payment: 12 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20121221 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20121221 |