EP1537197B1 - Utilisation de celluloses cationiques favorisant l'administration d'agents de soin pour tissus - Google Patents
Utilisation de celluloses cationiques favorisant l'administration d'agents de soin pour tissus Download PDFInfo
- Publication number
- EP1537197B1 EP1537197B1 EP03752219A EP03752219A EP1537197B1 EP 1537197 B1 EP1537197 B1 EP 1537197B1 EP 03752219 A EP03752219 A EP 03752219A EP 03752219 A EP03752219 A EP 03752219A EP 1537197 B1 EP1537197 B1 EP 1537197B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fabric care
- care benefit
- water insoluble
- mixtures
- mixture
- 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
- 239000004744 fabric Substances 0.000 title claims abstract description 91
- 230000008901 benefit Effects 0.000 title claims abstract description 56
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 45
- 229920002678 cellulose Polymers 0.000 title claims abstract description 31
- 235000010980 cellulose Nutrition 0.000 title description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 230000002708 enhancing effect Effects 0.000 claims abstract description 22
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 239000001913 cellulose Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- -1 polydimethylsiloxane Polymers 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 229910052990 silicon hydride Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 description 31
- 239000003599 detergent Substances 0.000 description 25
- 102000004190 Enzymes Human genes 0.000 description 19
- 108090000790 Enzymes Proteins 0.000 description 19
- 238000000151 deposition Methods 0.000 description 15
- 230000008021 deposition Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 10
- 102000004882 Lipase Human genes 0.000 description 9
- 108090001060 Lipase Proteins 0.000 description 9
- 239000004367 Lipase Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 235000019421 lipase Nutrition 0.000 description 8
- 239000004753 textile Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 108091005804 Peptidases Proteins 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 238000004900 laundering Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000002979 fabric softener Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 239000004365 Protease Substances 0.000 description 4
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 239000006187 pill Substances 0.000 description 4
- 229920005646 polycarboxylate Polymers 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 108010056079 Subtilisins Proteins 0.000 description 3
- 102000005158 Subtilisins Human genes 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 230000001153 anti-wrinkle effect Effects 0.000 description 3
- 229920003086 cellulose ether Polymers 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 2
- 239000004382 Amylase Substances 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical group O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000375 suspending agent Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical class CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000194108 Bacillus licheniformis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102100027612 Kallikrein-11 Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004907 Macro-emulsion Substances 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
- 239000004677 Nylon Substances 0.000 description 1
- SXKQTYJLWWQUKA-UHFFFAOYSA-N O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O Chemical compound O.O.O.O.O.O.O.O.O.O.OB(O)O.OB(O)O.OB(O)O.OB(O)O SXKQTYJLWWQUKA-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 241000145542 Pseudomonas marginata Species 0.000 description 1
- 101000968491 Pseudomonas sp. (strain 109) Triacylglycerol lipase Proteins 0.000 description 1
- 241000589614 Pseudomonas stutzeri Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 241000223258 Thermomyces lanuginosus Species 0.000 description 1
- 101710152431 Trypsin-like protease Proteins 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 230000001851 biosynthetic effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000005620 boronic acid group Chemical class 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- CMFFZBGFNICZIS-UHFFFAOYSA-N butanedioic acid;2,3-dihydroxybutanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O.OC(=O)C(O)C(O)C(O)=O CMFFZBGFNICZIS-UHFFFAOYSA-N 0.000 description 1
- HXDRSFFFXJISME-UHFFFAOYSA-N butanedioic acid;2,3-dihydroxybutanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)C(O)C(O)C(O)=O HXDRSFFFXJISME-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940124447 delivery agent Drugs 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 235000019645 odor Nutrition 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
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 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
- 239000003826 tablet Substances 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M toluenesulfonate group Chemical class C=1(C(=CC=CC1)S(=O)(=O)[O-])C LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- GDJZZWYLFXAGFH-UHFFFAOYSA-M xylenesulfonate group Chemical group C1(C(C=CC=C1)C)(C)S(=O)(=O)[O-] GDJZZWYLFXAGFH-UHFFFAOYSA-M 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
- C11D3/3742—Nitrogen containing silicones
-
- 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
- C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid 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
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/329—Carbohydrate or derivatives thereof
Definitions
- the present invention relates to the use of cationic celluloses to enhance deposition of water insoluble fabric care benefit agents such as water insoluble silicone derivatives during laundering.
- Laundering textiles is a necessity in order to remove stains, odors and soils.
- textiles can undergo mechanical and chemical damage which can result in fabric wrinkles, color fading, dye transfer, pills/fuzz, fabric wear, fiber deterioration, stiffness, and other undesirable consumer issues. Therefore, many laundry products such as detergents, fabric conditioners, and other wash, rinse, and dryer added products, frequently include one or more fabric care benefit agents that are added in an attempt to reduce or prevent these consumer issues.
- fabric care benefit agents often provide limited benefits due to poor delivery efficiency on the fabrics or textiles during the laundering process.
- the affinity between these fabric care agents and fabrics/garments is typically very limited due to the lack of natural attractive forces between the fabric care agents and the fabrics. This is because most fabric care agents used in laundry products are formulated to be anionic or nonionic in order to avoid interaction with anionic surfactants which might lead to potential cleaning negatives. Since most textile fibers such as cotton, wool, silk, nylon, and the like carry a slightly anionic charge in the laundry solution, there are repulsive instead of attractive forces between the fabric care agent and the fabric resulting in poor delivery efficiency.
- water insoluble fabric care benefit agents examples of which include but are not limited to, water insoluble silicone derivatives and the like. Due to their water insolubility, water insoluble fabric care benefit agents are generally incorporated into laundry product formulations in some type of water stable form such as an emulsion, a latex, a dispersion, a suspension, or the like. When added to the laundry product in a water stable form, the water insoluble fabric care benefit agent becomes even more stable in solution. This is due to the existence of large amounts of surfactant that are present in laundry products.
- the surfactant in the laundry products tends to act as an emulsifying agent, dispersion agent, suspension agent, or the like thereby resulting in the further stabilization of the emulsion, dispersion, and/or suspension containing the water insoluble fabric care benefit agent.
- the affinity of the water insoluble fabric care benefit agent for the fabric is severely limited.
- the majority of the water insoluble fabric care benefit agent tends to stay in solution wherein it is discarded with the wash solution thereby limiting the amount of benefit agent available for deposition on the fabric.
- the laundry products of the present invention comprise at least one water insoluble fabric care benefit agent and at least one cationic cellulose delivery enhancing agent or deposition aid, as defined in the claims.
- laundry products of the present invention improve the fabric delivery efficiency of water insoluble fabric care benefit agents that are incorporated therein by the inclusion of the cationic cellulose delivery agents of the present invention. It has surprisingly been found that by using cationic celluloses as delivery enhancing agents, the delivery of the water insoluble fabric care benefit agent to the fabric is significantly enhanced, which would not otherwise be possible.
- the cationic celluloses may provide fabric care benefits by themselves, an amount of the cationic celluloses needed to deliver significant performance benefits is much larger than an amount of the cationic celluloses needed as a delivery enhancing agent.
- large amounts of cationic celluloses often have a negative affect on cleaning performance. The cleaning negative caused by the large amount of cationic celluloses will normally prohibit their application in laundry detergent embodiments as the benefit agents alone.
- the level of the cationic cellulose as the delivery enhancing agent the impact on cleaning is normally very limited.
- the addition of the cationic celluloses of the present invention into laundry products may provide significant improvement in the delivery/deposition of the water insoluble fabric care benefit agent on the fabric versus utilizing the water insoluble fabric care benefit agent alone.
- a laundry detergent containing cationic celluloses and the fabric care benefit agent are added in the washer, delivery/deposition enhancements of the water insoluble fabric care benefit agent on fabric of as much as 5 to 10 times the normal amount of benefit agent alone are observed.
- the delivery/deposition enhancements may be accomplished by mixing the cationic cellulose and the fabric care benefit agent together as a laundry additive of a fabric care composite or by formulating these two ingredients into laundry detergent or other laundry products.
- the present invention relates to the use of cationic celluloses to enhance deposition of water insoluble fabric care benefit agents that are water insoluble silicone derivatives during laundering.
- utilizing the cationic cellulose delivery enhancing agents of the present invention allows for improved delivery of the water insoluble fabric care benefit agent to the fabric so as to provide enhanced fabric softening, color protection, pill/fuzz reduction, anti-abrasion, anti-wrinkle, and other such benefits to garments and textiles.
- the cationic cellulose called the delivery enhancing agent, and the water insoluble fabric care benefit agent may be mixed together prior to formulating in, adding to, or using in conjunction with a laundry product composition.
- the two components may be formulated into laundry products separated with different orders of addition.
- the two components of the present invention may also be mixed together in situ after addition to the laundry product composition. Additionally, the two components may be applied directly to the fabric together or separately.
- the deposition of the water insoluble fabric care benefit agent on the fabric is significantly improved and in some instances doubled, (i.e.; utilizing the delivery enhancing agent of the present invention may increase the deposition of the water insoluble fabric care benefit agent on the fabric by potentially about 100% or more compared with using the water insoluble fabric care benefit agent alone).
- deposition on the fabric will increase by at least about 200%. Since the fabric care benefit is directly related to the amount of deposition of the fabric care benefit agent on the fabric, the performance of the water insoluble fabric care benefit agent on the fabric should theoretically increase proportionately by potentially about 100% and preferably by at least about 200%.
- the ratio of the delivery enhancing agent to the water insoluble fabric care benefit agent should be from about 1:50 to 1:1 and preferably from about 1:20 to 1:2.
- the two components can be premixed to form a stable composite prior to formulating into a laundry product or prior to adding to the laundry process or applying to a fabric.
- the two components can also be formulated into laundry products separately with different orders of addition.
- the two components may also be mixed together so as to form the fabric care composite of the present invention in situ after formulating into the laundry product or adding to the laundry process.
- delivery enhancing agent refers to any cationic cellulose or combination of cationic celluloses that significantly enhance the deposition of the water insoluble fabric care benefit agent onto the fabric during laundering.
- the delivery enhancing agent has a strong physical binding capability with the water insoluble fabric care benefit agent. It also has a very strong affinity to natural textile fibers, such as cotton fibers.
- An effective delivery enhancing agent preferably has a strong binding capability with the water insoluble fabric care benefit agents via physical forces such as van der Waals forces or non-covalent chemical bonds such as hydrogen bonding and/or ionic bonding. It preferably has a very strong affinity to natural textile fibers, particularly cotton fibers.
- the delivery enhancing agent should be water soluble and have a flexible molecular structure so that it can cover the water insoluble fabric care benefit agent particle surface or hold several particles together. Therefore, the delivery enhancing agent is preferably not cross-linked and preferably does not have a network structure as these both tend to lack molecular flexibility.
- the net charge of the delivery enhancing agent is preferably positive in order to overcome the repulsion between the fabric care benefit agent and the fabric since most fabrics are comprised of textile fibers that have a slightly negative charge in aqueous environments.
- fibers exhibiting a slightly negative charge in water include but are not limited to cotton, rayon, silk, wool, etc.
- the delivery enhancing agent is a cationic or amphoteric polymer.
- the amphoteric polymers will also have a net cationic charge, i.e., the total cationic charges on these polymers will exceed the total anionic charge.
- the degree of substitution of the cationic charge can be in the range of from about 0.01 (one cationic charge per 100 polymer repeating units) to 1.00 (one cationic charge on every polymer repeating unit) and preferably from about 0.01 to 0.20.
- the positive charges could be on the backbone of the polymers or the side chains of polymers.
- the degree of substitution of the cationic charge can be simply calculated by the cationic charges per 100 glucose repeating units.
- One cationic charge per 100 glucose repeating units equals to 1% charge density of the cationic celluloses.
- Preferred cationic celluloses for use herein include those which may or may not be hydrophobically-modified, having a molecular weight of from about 50,000 to about 2,000,000, more preferably from about 100,000 to about 1,000,000, and most preferably from about 200,000 to about 800,000.
- R 1 , R 2 , R 3 are each independently H, CH 3 , C 8-24 alkyl (linear or branched), or mixtures thereof; wherein n is from about 1 to about 10; Rx is H, CH 3 , C 8-24 alkyl (linear or branched), or mixtures thereof, wherein Z is a water soluble anion, preferably a chlorine ion and/or a bromine ion; R 5 is H, CH 3 , CH 2 CH 3 , or mixtures thereof; R 7 is CH 3 , CH 2 CH 3 , a phenyl group, a C 8-24 alkyl group (linear or branched), or mixture thereof; and R 8 and R 9 are each independently CH 3 , CH 2 CH 3 , phenyl, or mixtures thereof:
- Water-soluble anions useful herein include C8-C24 alkyl sulfates, C8-C24 alkyl alkoxy sulfates, preferably alkyl ethoxy sulfates, C8-C24 alkyl sulfonates, C8-C16 alkyl benzene sulfonates, xylene sulfonates, toluene sulfonates, cumene sulfonates, fatty alkyl carboxylates, chlorine ions, bromine ions, or mixtures thereof, while chlorine and/or bromine ions are preferred.
- the charge density of the cationic celluloses herein (as defined by the number of cationic charges per 100 glucose units) is preferably from about 0.5 % to about 60%, more preferably from about 1% to about 20%, and most preferably from about 2% to about 10%.
- Alkyl substitution on the anhydroglucose rings of the polymer ranges from about 0.01% to 5% per glucose unit, more preferably from about 0.05% to 2% per glucose unit, of the polymeric material.
- the cationic cellulose may lightly cross-linked with a dialdehyde such as glyoxyl to prevent forming lumps, nodules or other agglomerations when added to water at ambient temperatures.
- a dialdehyde such as glyoxyl
- the cationic cellulose ethers of Structural Formula I likewise include those which are commercially available and further include materials which can be prepared by conventional chemical modification of commercially available materials.
- Commercially available cellulose ethers of the Structural Formula I type include the JR 30M, JR 400, JR 125, LR 400 and LK 400 polymers, all of which are marketed by Dow Chemical.
- water insoluble fabric care benefit agent refers to any silicone derivatives that are water insoluble and can provide fabric care benefits such as fabric softening, color protection, pill/fuzz reduction, anti-abrasion, anti-wrinkle, and the like to garments and fabrics, particularly on cotton garments and fabrics, when an adequate amount of the material is present on the garment/fabric.
- fabric care benefits such as fabric softening, color protection, pill/fuzz reduction, anti-abrasion, anti-wrinkle, and the like to garments and fabrics, particularly on cotton garments and fabrics, when an adequate amount of the material is present on the garment/fabric.
- water insoluble fabric care benefit agents include water-insoluble silicone derivatives and mixtures thereof.
- water insoluble silicone derivatives are any silicone materials which are not soluble in water, but can be prepared as emulsions, latexes, dispersions, suspensions and the like with suitable surfactants before formulation of the laundry products.
- Any neat silicones that can be directly emulsified or dispersed into laundry products are also covered in the present invention since laundry products typically contain a number of different surfactants that can behave like emulsifiers, dispersing agents, suspension agents, etc. thereby aiding in the emulsification, dispersion, and/or suspension of the water insoluble silicone derivative.
- these silicone derivatives can provide one or more fabric care benefit to the fabric including anti-wrinkle, color protection, pill/fuzz reduction, anti-abrasion, fabric softening and the like.
- the water insoluble silicone derivatives include, but are not limited to 1) non-functionalized silicones such as polydimethylsiloxane (PDMS), including linear, grafted and cyclic structures and 2) functionalized silicones or copolymers with one or more different types of functional groups such as amino, alkoxy, alkyl, phenyl, polyether, acrylate, siliconhydride, mercaptoproyl, carboxylic acid, quaternized nitrogen, etc.
- PDMS polydimethylsiloxane
- functionalized silicones or copolymers with one or more different types of functional groups such as amino, alkoxy, alkyl, phenyl, polyether, acrylate, siliconhydride, mercaptoproyl, carboxylic acid, quaternized nitrogen, etc.
- the particle size can be in the range from about 1 nm to 100 microns and preferably from about 10 nm to about 10 microns including microemulsions ( ⁇ 150 nm), standard emulsions (about 200 nm to about 500 nm) and macroemulsions (about 1 micron to about 20 microns).
- Water soluble silicone derivatives are outside of the scope of the present invention.
- Non-limiting examples of commercially available water insoluble silicone derivatives include SM2125 commercially available from GE Silicones,and DC8822 and DC 200 Fluid both of which are commercially available from Dow Coming.
- a non-limiting list of optional components of the present invention includes laundry detergents, fabric conditioners, and other wash, rinse, and dryer added products.
- the laundry products may comprise from about 0.1% to about 20% of the water insoluble fabric care benefit agent, preferably from about 0.2% to about 10%.
- the laundry products may also comprise from about 0.01% to about 5% of the delivery enhancing agent, preferably from about 0.02% to about 2%.
- Conventional components of fabric conditioners include but are not limited to surfactants and the like.
- detergent compositions include but are not limited to surfactants, bleaches and bleach activators, enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, non-builder alkalinity sources, chelating agents, organic and inorganic fillers, solvents, hydrotropes, optical brighteners, dyes, perfumes, and modified cellulose ether fabric treatment agents.
- the fabric care benefit agents or delivery enhancing agent of the present invention may be a component of or added to a detergent composition or a fabric conditioner.
- the detergent composition may be in the form of a granule, liquid, or tablet.
- Detergent compositions of the present invention may be made in accordance with U.S. Patent Nos. 6,274,540 and 6,306,817 and WIPO Publication Nos. WO 01/16237 published March 8, 2001 and WO 01/16263 published on March 8,2001 .
- the laundry products of the present invention may comprise from 5% to 50% by weight of surfactant.
- Detersive surfactants utilized can be of the anionic, nonionic, zwitterionic, ampholytic or cationic type or can comprise compatible mixtures of these types.
- Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972 , U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975 , U.S. Patent 4,222,905, Cockrell, issued September 16, 1980 , and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980 .
- Anionic and nonionic surfactants are preferred.
- Useful anionic surfactants can themselves be of several different types.
- water-soluble salts of the higher fatty acids i.e., "soaps"
- 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.
- non-soap anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- this group of synthetic surfactants are a) the sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to 15, preferably 1 to 6 ethoxylate moieties; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, 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 11-13 LAS.
- Preferred nonionic surfactants are those 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 about 5 to about 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 of the formula: wherein R is a C 9-17 alkyl or alkenyl, R 1 is a methyl group and Z is glycidyl derived from a reduced sugar or alkoxylated derivative thereof. 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 2,965,576 and Schwartz, U.S. Patent 2,703,798 ,
- compositions may also comprise from about 0.1% to 80% by weight of a builder.
- a builder Preferably such compositions in liquid form will comprise from about 1% to 10% by weight of the builder component.
- compositions in granular form will comprise from about 1% to 50% by weight of the builder component.
- Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.
- Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
- polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
- Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in U.S.
- Particularly preferred polycarboxylate builders are the oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987 .
- nonphosphorus, inorganic builders include the silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates including zeolites. Such materials and their use as detergent builders are more fully discussed in Corkill et al, U. S. Patent No. 4,605,509 . Also, crystalline layered silicates such as those discussed in Corkill et al, U. S. Patent No. 4,605,509 are suitable for use in the detergent compositions of this invention.
- the laundry products of the present invention may also comprise an enzyme that is a amylase, lipase, selected protease enzyme, or mixtures thereof. Enzymes are normally incorporated into detergent compositions at levels sufficient to provide a "cleaning-effective amount".
- cleaning-effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics.
- the laundry product compositions of the present invention may contain up to about 5 mg by weight, more typically from about 0.01 mg to about 3 mg, of active enzyme per gram of the detergent composition.
- compositions herein will typically comprise from about 0.001% to about 5%, preferably from about 0.01% to about 1% by weight of the composition, of a commercial enzyme preparation.
- Protease enzymes are preferably present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units. (AU) of activity per gram of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
- Selected proteases which are useful herein include the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
- a preferred protease is obtained from a strain of Bacillus , having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE ® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo .
- Other suitable proteases include ALCALASE ® and SAVINASE ® from Novo and MAXATASE ® from International Bio-Synthetics, Inc., The Netherlands.
- a protease having decreased adsorption and increased hydrolysis may be included in the compositions herein, as described in WO 9507791 to Procter & Gamble .
- Another recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo .
- amylase Any known amylase may be included in the compositions of the present invention.
- Suitable lipase enzymes for use herein include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034 . See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978 . This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” or "Amano-P.” Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
- lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
- LIPOLASE ® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947 is a preferred lipase for use herein.
- compositions of the present invention contain a compatible enzyme
- the compositions preferably also contain an effective enzyme stabilizing system.
- the enzyme-containing compositions herein may therefore optionally also comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
- the enzyme stabilizing system can be any stabilizing system which is compatible with the enzymes useful herein. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of enzymes.
- Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, or mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.
- the laundry product compositions herein are formulated as liquid laundry detergents.
- the liquid laundry detergent compositions preferably comprise from about 3% to about 98%, preferably from about 15% to about 95%, by weight of the liquid detergent composition, of an aqueous liquid carrier which is preferably water.
- the liquid laundry compositions according to the present invention should provide a wash solution pH from about 6 to about 10, more preferably from about 7 to about 9, in order to maintain a preferred stain removal performance by the liquid laundry products according to the present invention.
- the cleaning compositions may contain alkalinizing agents, pH control agents and/or buffering agents.
- the density of the laundry detergent compositions herein preferably ranges from about 400 to about 1200 g/litre, more preferably from about 500 to about 1100 g/litre of composition measured at 20°C.
- laundry product formulations may be made by traditional methods and means as known to one of ordinary skill in the art.
- Example 2 Wt% Wt% C12-15alkyl polyethoxylate sulfate 12.31 12.31 Linear alkylbenzene sulfonate 5.39 5.39 Ethanol 3.44 3.44 Monoethanolamine 1.49 1.49 Propandiol 6.61 6.61 C12-13Alkyl polyethoxylate (9) 2.18 2.18 C12-14 alkyl dimethylamine N-oxide 0.73 0.73 C12-14 fatty acid 1.98 1.98 Citric acid 3.96 3.96 Borax 1.50 1.50 Sodium hydroxide (to pH 8.0) 5.00 5.00 Cationic Cellulose* 0.10 0.20 PDMS** 1.50 1.50 Water, perfume, enzymes, suds suppressor, brightener, additional deposition aid & other optional ingredients to 100% to 100% * Supplied by Dow Chemicals. ** polydimethylsiloxane, supplied by Dow Coming
- Example 4 Wt % Wt % C12 linear alkylbenzene sulfonate 3.44 3.44 C16-17 methyl branched alkyl sulfate 9.41 9.41 C14-15 alkyl sulfate 4.04 4.04 AlSil 37.37 37.37 Na 2 CO 3 22.34 22.34 PEG 2.53 2.53 DTPA 0.72 0.72 NaPAA 1.03 1.03 Perborate 2.56 2.56 Nonanoyloxybenzenesulfonate 1.92 1.92 Modified cellulose 1.54 1.54 Cationic Cellulose* 0.15 0.20 PDMS (100k cSt)** 1.50 2.50 Water, perfume, enzymes, suds suppressor, brightener, additional deposition aid & other optional ingredients to 100% to 100% * Supplied by Dow Chemicals ** polydimethylsiloxane supplied by Dow Coming
- Example 6 Wt % Wt % Di-(tallowyl-oxy-ethyl) dimethyl ammonium chloride. 18.0 24.0 NH 4 Cl 0.2 0.2 Cationic Cellulose* 0.2 0.3 PDMS (100 k cSt)** 3.0 2.0 Water, perfume and minors To 100% To 100% * Supplied by Dow Chemicals ** polydimethylsiloxane supplied by Dow Coming
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Cosmetics (AREA)
Claims (6)
- Composition de produit pour le lavage du linge comprenant un mélange stable :a) de 0,1 % à 10 %, en poids de la composition, d'au moins un agent bénéfique pour le soin des tissus insoluble dans l'eau; etb) de 0,01 % à 5 %, en poids de la composition, d'au moins un agent améliorant la libération qui est une cellulose cationique,dans laquelle l'agent bénéfique pour le soin des tissus insoluble dans l'eau est un dérivé de silicone insoluble dans l'eau ou un de ses mélanges, et dans laquelle la composition comprend de 5 % à 50 % en poids d'un agent tensioactif choisi parmi des alkylbenzène sulfonates de sodium et de potassium dans lesquels le groupe alkyle contient de 9 à 15 atomes de carbone dans une configuration en chaîne linéaire ou ramifiée.
- Composition de produit pour le lavage du ligne selon la revendication 1, dans laquelle l'agent bénéfique pour le soin des tissus insoluble dans l'eau a une taille de particule allant d'environ 1 nm à 100 microns.
- Composition de produit pour le lavage du linge selon l'une quelconque des revendications précédentes, dans laquelle l'agent bénéfique pour le soin des tissus insoluble dans l'eau est une silicone non fonctionnalisée ayant une structure linéaire, greffée ou cyclique; une silicone fonctionnalisée ; un copolymère avec un ou plusieurs types différents de groupes fonctionnels qui est un amino, un alkoxy, un alkyle, un phényle, un polyéther, un acrylate, un siliconhydrure, un mercaptoproyle, un acide carboxylique, un azote quaternaire, ou leurs mélanges, ou un mélange de ceux-ci, plus préférablement un polydiméthylsiloxane.
- Composition de produit pour le lavage du linge selon l'une quelconque des revendications précédentes, dans laquelle le mélange stable est formé in situ.
- Composition de produit pour le lavage du linge selon la revendication 1, dans laquelle le rapport de l'agent améliorant la libération et de l'agent bénéfique pour le soin des tissus va de 1:50 à 1:1,
- Composition de produit pour le lavage du linge selon l'une quelconque des revendications précédentes, dans laquelle la cellulose cationique est de structure :
R8 et R9 sont chacun indépendamment CH3, CH2CH3, un phényle ou leurs mélanges :
R4 est H,
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08152893A EP2210933A1 (fr) | 2002-09-09 | 2003-09-09 | Utilisation de celluloses cationiques favorisant l'administration d'agents de soin pour tissus |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US40909102P | 2002-09-09 | 2002-09-09 | |
US409091P | 2002-09-09 | ||
US10/375,792 US6897190B2 (en) | 2002-02-28 | 2003-02-26 | Detergent compositions including dispersible polyolefin wax and method for using same |
US375792 | 2003-02-26 | ||
PCT/US2003/028421 WO2004022686A1 (fr) | 2002-09-09 | 2003-09-09 | Utilisation de celluloses cationiques favorisant l'administration d'agents de soin pour tissus |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1537197A1 EP1537197A1 (fr) | 2005-06-08 |
EP1537197B1 true EP1537197B1 (fr) | 2008-03-19 |
Family
ID=31981196
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08152893A Withdrawn EP2210933A1 (fr) | 2002-09-09 | 2003-09-09 | Utilisation de celluloses cationiques favorisant l'administration d'agents de soin pour tissus |
EP03752194A Expired - Lifetime EP1537196B1 (fr) | 2002-09-09 | 2003-09-09 | Utilisation de celluloses cationiques pour ameliorer la liberation d'agents traitants d'entretien de textiles |
EP03752219A Expired - Lifetime EP1537197B1 (fr) | 2002-09-09 | 2003-09-09 | Utilisation de celluloses cationiques favorisant l'administration d'agents de soin pour tissus |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08152893A Withdrawn EP2210933A1 (fr) | 2002-09-09 | 2003-09-09 | Utilisation de celluloses cationiques favorisant l'administration d'agents de soin pour tissus |
EP03752194A Expired - Lifetime EP1537196B1 (fr) | 2002-09-09 | 2003-09-09 | Utilisation de celluloses cationiques pour ameliorer la liberation d'agents traitants d'entretien de textiles |
Country Status (11)
Country | Link |
---|---|
EP (3) | EP2210933A1 (fr) |
JP (2) | JP4145874B2 (fr) |
CN (2) | CN1678723A (fr) |
AT (2) | ATE389708T1 (fr) |
AU (2) | AU2003270521A1 (fr) |
BR (2) | BR0314074A (fr) |
CA (2) | CA2495117A1 (fr) |
DE (2) | DE60320655T2 (fr) |
ES (2) | ES2302939T3 (fr) |
MX (2) | MXPA05002610A (fr) |
WO (2) | WO2004022685A1 (fr) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7226900B2 (en) | 2003-06-16 | 2007-06-05 | The Proctor & Gamble Company | Liquid laundry detergent composition containing boron-compatible cationic deposition aids |
GB0514147D0 (en) * | 2005-07-11 | 2005-08-17 | Unilever Plc | Laundry treatment compositions |
RU2421506C2 (ru) * | 2006-04-13 | 2011-06-20 | Дзе Проктер Энд Гэмбл Компани | Жидкие моющие средства для стирки, содержащие катионный полимер гидроксиэтилцеллюлозы |
JP2010523833A (ja) * | 2007-04-02 | 2010-07-15 | ザ プロクター アンド ギャンブル カンパニー | 布地ケア組成物 |
US7576048B2 (en) | 2007-04-04 | 2009-08-18 | The Procter & Gamble Company | Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer |
JP5364252B2 (ja) * | 2007-08-02 | 2013-12-11 | ライオン株式会社 | 粒状洗剤組成物 |
DE102010028378A1 (de) * | 2010-04-29 | 2011-11-03 | Henkel Ag & Co. Kgaa | Polyelektrolyt-Komplexe als schmutzablösevermögende Wirkstoffe |
ES2394066T3 (es) * | 2010-06-24 | 2013-01-16 | The Procter & Gamble Company | Composiciones estables que comprenden polímero de celulosa catiónica y celulasa |
EP2399978B2 (fr) * | 2010-06-24 | 2020-11-25 | The Procter and Gamble Company | Compositions liquides stables non aqueuses comprenant un polymère cationique sous forme particulaire |
BR112015008917B1 (pt) | 2012-11-20 | 2022-02-01 | Unilever Ip Holdings B.V. | Composição detergente para lavar roupa |
EP3441449A1 (fr) * | 2017-08-11 | 2019-02-13 | The Procter & Gamble Company | Utilisation de la combinaison d'un polymère de polysaccharide cationique et d'un tensio-actif anionique |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3580853A (en) * | 1967-09-27 | 1971-05-25 | Procter & Gamble | Detergent compositions containing particle deposition enhancing agents |
US3664961A (en) | 1970-03-31 | 1972-05-23 | Procter & Gamble | Enzyme detergent composition containing coagglomerated perborate bleaching agent |
US3919678A (en) | 1974-04-01 | 1975-11-11 | Telic Corp | Magnetic field generation apparatus |
US4222905A (en) | 1978-06-26 | 1980-09-16 | The Procter & Gamble Company | Laundry detergent compositions having enhanced particulate soil removal performance |
US4237016A (en) * | 1977-11-21 | 1980-12-02 | The Procter & Gamble Company | Textile conditioning compositions with low content of cationic materials |
US4239659A (en) | 1978-12-15 | 1980-12-16 | The Procter & Gamble Company | Detergent compositions containing nonionic and cationic surfactants, the cationic surfactant having a long alkyl chain of from about 20 to about 30 carbon atoms |
GB9216758D0 (en) * | 1992-08-07 | 1992-09-23 | Unilever Plc | Detergent composition |
US5476660A (en) * | 1994-08-03 | 1995-12-19 | Lever Brothers Company, Division Of Conopco, Inc. | Deposition of materials to surfaces using zwitterionic carrier particles |
HUP0002572A3 (en) | 1997-07-21 | 2001-04-28 | Procter & Gamble | Detergent compositions containing mixtures of crystallinity-disrupted surfactants |
PH11998001775B1 (en) | 1997-07-21 | 2004-02-11 | Procter & Gamble | Improved alkyl aryl sulfonate surfactants |
US6126954A (en) * | 1999-04-05 | 2000-10-03 | Unilever Home & Personal Care Usa, Division Of Conopco | Liquid compositions comprising stable emulsion of small particle skin benefit agent |
DE19926863A1 (de) * | 1999-06-12 | 2000-12-14 | Henkel Kgaa | Verwendung von partiell oxidiertem Polyethylen als Bügelhilfe in flüssigen wäßrigen Weichspülern |
WO2001016263A2 (fr) | 1999-08-27 | 2001-03-08 | The Procter & Gamble Company | Disponibilite controlee de composants de formulation, compositions et procede de blanchissage utilisant ces produits |
DE19941132A1 (de) | 1999-08-30 | 2001-03-01 | Basf Ag | Verfahren zur kontinuierlichen Herstellung von Glutaraldehyd |
-
2003
- 2003-09-09 BR BR0314074-1A patent/BR0314074A/pt not_active IP Right Cessation
- 2003-09-09 EP EP08152893A patent/EP2210933A1/fr not_active Withdrawn
- 2003-09-09 MX MXPA05002610A patent/MXPA05002610A/es unknown
- 2003-09-09 CN CN03821072.XA patent/CN1678723A/zh active Pending
- 2003-09-09 MX MXPA05002611A patent/MXPA05002611A/es unknown
- 2003-09-09 JP JP2004534811A patent/JP4145874B2/ja not_active Expired - Fee Related
- 2003-09-09 EP EP03752194A patent/EP1537196B1/fr not_active Expired - Lifetime
- 2003-09-09 JP JP2004534807A patent/JP4283224B2/ja not_active Expired - Fee Related
- 2003-09-09 DE DE60320655T patent/DE60320655T2/de not_active Expired - Lifetime
- 2003-09-09 CA CA002495117A patent/CA2495117A1/fr not_active Abandoned
- 2003-09-09 ES ES03752219T patent/ES2302939T3/es not_active Expired - Lifetime
- 2003-09-09 AT AT03752219T patent/ATE389708T1/de not_active IP Right Cessation
- 2003-09-09 AU AU2003270521A patent/AU2003270521A1/en not_active Abandoned
- 2003-09-09 AT AT03752194T patent/ATE393812T1/de not_active IP Right Cessation
- 2003-09-09 EP EP03752219A patent/EP1537197B1/fr not_active Expired - Lifetime
- 2003-09-09 AU AU2003270497A patent/AU2003270497A1/en not_active Abandoned
- 2003-09-09 DE DE60319845T patent/DE60319845T2/de not_active Expired - Lifetime
- 2003-09-09 BR BR0314147-0A patent/BR0314147A/pt not_active IP Right Cessation
- 2003-09-09 WO PCT/US2003/028346 patent/WO2004022685A1/fr active Application Filing
- 2003-09-09 WO PCT/US2003/028421 patent/WO2004022686A1/fr active Application Filing
- 2003-09-09 ES ES03752194T patent/ES2305492T3/es not_active Expired - Lifetime
- 2003-09-09 CA CA002495323A patent/CA2495323A1/fr not_active Abandoned
- 2003-09-09 CN CN03821073.8A patent/CN1678724A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
BR0314147A (pt) | 2005-07-12 |
CA2495323A1 (fr) | 2004-03-18 |
CA2495117A1 (fr) | 2004-03-18 |
WO2004022686A1 (fr) | 2004-03-18 |
CN1678724A (zh) | 2005-10-05 |
MXPA05002610A (es) | 2005-05-05 |
AU2003270497A1 (en) | 2004-03-29 |
CN1678723A (zh) | 2005-10-05 |
JP2005536618A (ja) | 2005-12-02 |
JP4283224B2 (ja) | 2009-06-24 |
EP2210933A1 (fr) | 2010-07-28 |
EP1537197A1 (fr) | 2005-06-08 |
AU2003270521A1 (en) | 2004-03-29 |
DE60320655D1 (de) | 2008-06-12 |
DE60319845D1 (de) | 2008-04-30 |
EP1537196B1 (fr) | 2008-04-30 |
ES2302939T3 (es) | 2008-08-01 |
DE60319845T2 (de) | 2009-03-05 |
BR0314074A (pt) | 2005-07-05 |
DE60320655T2 (de) | 2009-06-04 |
ATE389708T1 (de) | 2008-04-15 |
JP4145874B2 (ja) | 2008-09-03 |
ES2305492T3 (es) | 2008-11-01 |
WO2004022685A1 (fr) | 2004-03-18 |
MXPA05002611A (es) | 2005-05-05 |
ATE393812T1 (de) | 2008-05-15 |
JP2005537408A (ja) | 2005-12-08 |
EP1537196A1 (fr) | 2005-06-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7056879B2 (en) | Using cationic celluloses to enhance delivery of fabric care benefit agents | |
US7056880B2 (en) | Using cationic celluloses to enhance delivery of fabric care benefit agents | |
EP2004785B1 (fr) | Détergents liquides à lessive contenant un polymère cellulosique cationique hydroxyéthyle | |
US7576048B2 (en) | Liquid laundry detergents containing cationic hydroxyethyl cellulose polymer | |
EP1224253B1 (fr) | Compositions detergentes lessivielles prenant soin des tissus | |
US6897190B2 (en) | Detergent compositions including dispersible polyolefin wax and method for using same | |
US20020077265A1 (en) | Laundry articles and methods for care of fabrics or combined cleaning and care of fabrics | |
CA2276580C (fr) | Compositions de detergent a lessive contenant des fixatifs de colorant | |
EP1537197B1 (fr) | Utilisation de celluloses cationiques favorisant l'administration d'agents de soin pour tissus | |
US6956017B1 (en) | Laundry detergent compositions with fabric care | |
MXPA99006226A (en) | Laundry detergent compositions comprising dye fixatives |
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: 20050211 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK |
|
DAX | Request for extension of the european patent (deleted) | ||
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: LEYENDECKER, MARY, RUTH Inventor name: KINDEL, PAUL, FRANCIS Inventor name: WANG, JIPING Inventor name: PANANDIKER, RAJAN, KESHAV |
|
17Q | First examination report despatched |
Effective date: 20051018 |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: LEYENDECKER, MARY, RUTH Inventor name: KINDEL, PAUL, FRANCIS Inventor name: WANG, JIPING Inventor name: PANANDIKER, RAJAN, KESHAV |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR |
|
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 |
|
REF | Corresponds to: |
Ref document number: 60319845 Country of ref document: DE Date of ref document: 20080430 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20080319 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2302939 Country of ref document: ES Kind code of ref document: T3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: 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: 20080319 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI 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: 20080319 |
|
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: 20080619 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20080319 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20080319 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: 20080826 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO 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: 20080319 |
|
ET | Fr: translation filed | ||
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 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20080319 |
|
26N | No opposition filed |
Effective date: 20081222 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20080619 Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080930 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20080319 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
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: 20080909 |
|
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: 20080319 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080930 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080930 |
|
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: 20080909 Ref country code: HU 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: 20080920 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20080319 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20080620 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20120920 Year of fee payment: 10 Ref country code: FR Payment date: 20120910 Year of fee payment: 10 Ref country code: ES Payment date: 20120921 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20120913 Year of fee payment: 10 Ref country code: BE Payment date: 20121001 Year of fee payment: 10 |
|
BERE | Be: lapsed |
Owner name: THE PROCTER & GAMBLE CY Effective date: 20130930 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20140401 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20140530 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130930 |
|
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: 20130930 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20130909 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140401 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20150709 |
|
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: 20130910 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20190827 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20190906 Year of fee payment: 17 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60319845 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200909 |
|
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: 20210401 |
|
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: 20200909 |