EP3390607A1 - Penta-built liquid detergent composition - Google Patents
Penta-built liquid detergent compositionInfo
- Publication number
- EP3390607A1 EP3390607A1 EP16829240.7A EP16829240A EP3390607A1 EP 3390607 A1 EP3390607 A1 EP 3390607A1 EP 16829240 A EP16829240 A EP 16829240A EP 3390607 A1 EP3390607 A1 EP 3390607A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- detergent composition
- salt
- builder
- sodium
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 92
- 239000003599 detergent Substances 0.000 title claims abstract description 57
- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000004753 textile Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004472 Lysine Substances 0.000 claims abstract description 10
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- BPSYZMLXRKCSJY-UHFFFAOYSA-N 1,3,2-dioxaphosphepan-2-ium 2-oxide Chemical compound O=[P+]1OCCCCO1 BPSYZMLXRKCSJY-UHFFFAOYSA-N 0.000 claims abstract description 9
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 8
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- -1 alkali metal salts Chemical class 0.000 claims description 35
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 claims description 14
- CIEZZGWIJBXOTE-UHFFFAOYSA-N 2-[bis(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)C(C)N(CC(O)=O)CC(O)=O CIEZZGWIJBXOTE-UHFFFAOYSA-N 0.000 claims description 14
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 14
- 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 claims description 14
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 claims description 14
- 229960003330 pentetic acid Drugs 0.000 claims description 14
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 8
- 150000005215 alkyl ethers Chemical class 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- JHIDGGPPGFZMES-UHFFFAOYSA-N acetic acid;n-(2-aminoethyl)hydroxylamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.NCCNO JHIDGGPPGFZMES-UHFFFAOYSA-N 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 229940000635 beta-alanine Drugs 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 229960002989 glutamic acid Drugs 0.000 claims description 7
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229940077388 benzenesulfonate Drugs 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000344 soap Substances 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 239000002304 perfume Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- KRTNITDCKAVIFI-UHFFFAOYSA-N tridecyl benzenesulfonate Chemical compound CCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 KRTNITDCKAVIFI-UHFFFAOYSA-N 0.000 claims description 3
- FKKAGFLIPSSCHT-UHFFFAOYSA-N 1-dodecoxydodecane;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC FKKAGFLIPSSCHT-UHFFFAOYSA-N 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 claims description 2
- 239000000417 fungicide Substances 0.000 claims description 2
- 230000002070 germicidal effect Effects 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- XZZDWCJZCAQFDF-UHFFFAOYSA-N sodium;tridecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 XZZDWCJZCAQFDF-UHFFFAOYSA-N 0.000 claims 1
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 abstract 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 24
- 238000009472 formulation Methods 0.000 description 17
- 229910019142 PO4 Inorganic materials 0.000 description 15
- 235000021317 phosphate Nutrition 0.000 description 15
- 239000010452 phosphate Substances 0.000 description 12
- 235000019832 sodium triphosphate Nutrition 0.000 description 12
- 229920002125 SokalanĀ® Polymers 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 235000017550 sodium carbonate Nutrition 0.000 description 10
- 229920000058 polyacrylate Polymers 0.000 description 9
- 229960004106 citric acid Drugs 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 150000002191 fatty alcohols Chemical group 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229940117927 ethylene oxide Drugs 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229940043348 myristyl alcohol Drugs 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229940045990 sodium laureth-2 sulfate Drugs 0.000 description 2
- GUQPDKHHVFLXHS-UHFFFAOYSA-M sodium;2-(2-dodecoxyethoxy)ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOS([O-])(=O)=O GUQPDKHHVFLXHS-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 229940012831 stearyl alcohol Drugs 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000579895 Chlorostilbon Species 0.000 description 1
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000015779 HDL Lipoproteins Human genes 0.000 description 1
- 108010010234 HDL Lipoproteins Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- MQNVHUZWFZKETG-UHFFFAOYSA-N P1(OCCCCCO1)=O.NCCNCCN Chemical compound P1(OCCCCCO1)=O.NCCNCCN MQNVHUZWFZKETG-UHFFFAOYSA-N 0.000 description 1
- WFRXSOIFNFJAFL-UHFFFAOYSA-N P1(OCCCCO1)=O.C(CN)N Chemical compound P1(OCCCCO1)=O.C(CN)N WFRXSOIFNFJAFL-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000000692 Student's t-test Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 239000002671 adjuvant Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229910052876 emerald Inorganic materials 0.000 description 1
- 239000010976 emerald Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000373 fatty alcohol group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- 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
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C11D2111/12—
Definitions
- the present invention relates to an aqueous, phosphate-free, structured liquid detergent composition, in particular a heavy duty liquid detergent (HDL) that comprises a builder system, a surfactant system and water, wherein the builder system comprises five separate builder components.
- HDL heavy duty liquid detergent
- the invention further relates to methods for washing of textiles using the detergents of the invention.
- Liquid detergent compositions are well-known in the art and widely used. Over recent years, the have become more and more popular with the consumers because they offer a number of advantages over solid compositions, including, for example, the ease of dosing, dispensing and dissolving into a laundering liquor. In addition, they are perceived to be safer and less harsh to the textiles and environment compared to solid compositions. In particular for laundering colored fabrics they have gained popularity ever since their introduction on the market.
- liquid detergent compositions in particular phosphate-free heavy duty liquid (HDL) detergents suffer from physical and chemical instability and viscosity problems. This is particularly problematic for highly concentrated formulations.
- HDL detergents have been introduced as early as the 1970's, the known stable formulations rely on the use of phosphates, in particular sodium tripolyphosphate (STPP), to form structured liquids containing high levels of builders and surfactants.
- STPP sodium tripolyphosphate
- multilayered vesicles are formed that stabilize the formulation and prevent precipitation of the anionic surfactants by the builder components. These structures are stable and can be characterized by microscopic examination under polarized light and conductivity measurements.
- STPP was particularly suited to formation of vesicles with sodium alkylbenzene sulfonate (sodium LAS).
- STPP was well established as a builder in detergent powders and acts as a chelating agent, inhibits soil re- deposition during the wash and boosts overall detergency.
- the result of the use of STPP was the development of high performance and low cost HDL.
- environmental concerns over the use of phosphates, including STPP, in laundry detergents have resulted in phosphate use being banned in some countries and a negative public image in most developed markets. While alternatives to STPP, such as zeolite, sodium citrate, and sodium carbonate, are known, these show poor performance relative to phosphate built HDL.
- phosphate-free, structured HDL detergents that have comparable performance as the previously used phosphate-based formulations. Accordingly, it is an object of the present invention to meet this need by providing an aqueous, phosphate-free, structured liquid detergent composition, in particular a HDL detergent that exhibits the desired performance.
- this object can be met by a composition that comprises a specific builder system, a surfactant system and water. It has been demonstrated that such a detergent shares a similar washing performance as the previously used STPP-containing compositions.
- the present invention therefore relates to an aqueous, phosphate-free, structured liquid detergent composition
- a surfactant system e.g., sodium bicarbonate
- a builder system e.g., sodium bicarbonate
- water e.g., sodium bicarbonate
- C at least one aminocarboxylate, preferably selected from the group consisting of L- glutamic acid ā , ā -diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine ā , ā '-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine ā , ā -diacetic acid, hydroxyethylenediamine triacetic acid (HEDTA), and alkali metal salts thereof, more preferably GLDA tetrasodium salt;
- GLDA L- glutamic acid ā , ā -diacetic acid
- MGDA methyl glycine diacetic acid
- IDS imino disuccinic acid
- EDDS ethylenediamine ā , ā '-disuccinic acid
- DTPA diethylenetriamine pentaacetic acid
- HEDTA hydroxyethylenediamine triacetic
- the invention relates to methods for cleaning textiles, wherein a washing liquor containing the liquid detergent composition of the present invention contacts the textile in at least one method step.
- the invention also encompasses the use of a composition comprising
- C at least one aminocarboxylate, preferably selected from the group consisting of L- glutamic acid ā , ā -diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine ā , ā '-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine ā , ā -diacetic acid, hydroxyethylenediamine triacetic acid (HEDTA), and alkali metal salts thereof, more preferably GLDA tetrasodium salt;
- GLDA L- glutamic acid ā , ā -diacetic acid
- MGDA methyl glycine diacetic acid
- IDS imino disuccinic acid
- EDDS ethylenediamine ā , ā '-disuccinic acid
- DTPA diethylenetriamine pentaacetic acid
- HEDTA hydroxyethylenediamine triacetic
- At least one relates to one or more, i.e. 1 , 2, 3, 4, 5, 6, 7, 8, 9, or more. If used in combination with a compound, the term does not relate to the absolute number of molecules but rather to the number of different types of said compound. "At least one inorganic builderā thus means that at least one type but that also 2 or more different inorganic builder types can be present.
- viscosities referred to herein are viscosities measured at 20Ā°C by a Brookfield LVT, Spindle No. 3 at 12 rpm.
- Free of means that the referenced composition does not contain more than 0.5 wt.%, preferably no more than 0.1 wt.%, more preferably no more than 0.05 wt.% of said component relative to the total weight of the composition. Most preferably, said component is not contained at all.
- the detergent compositions of the present invention can be used as detergents for textiles, carpets or natural fibers.
- the detergents disclosed herein are heavy duty liquid (HDL) detergents.
- the present invention is based on the inventors' surprising finding, that by use of the disclosed builder system structured liquid detergent compositions may be formed that have the desired washing performance.
- Washing performance relates to the removal of stains, in particular stains sensitive to surfactants.
- the removal can be evaluated by measuring a brightening of the stain either instrumentally or by visual inspection.
- Structured liquids are widely used in the field of detergents. They can either be internally structured by one or more of the primary ingredients, such as the surfactants, and/or by using secondary additives, such as certain polymers and/or silicates. Structuring is used to endow the composition with properties such as a turbid appearance or certain flow properties. Such structured liquids may also contain suspended solids. While structured liquids provide more formulation flexibility compared to isotropic liquids, they often suffer from stability and viscosity problems. The presently disclosed formulations, however, provide for compositions that have the desired viscosities while at the same time showing good stability.
- the liquid detergent compositions of the invention are internally structured in that the surfactant system leads to formation of multilayered vesicles.
- Structured as used herein, therefore means that the compositions are preferably internally structured by formation of multilayered vesicles.
- Multilayered vesicles preferably relates to essentially spherical vesicles that have a multilayered, typically double-layered, shell formed of molecules comprising hydrophobic moieties, with said hydrophobic moieties arranged such that they face each other while the more hydrophilic parts of the molecules face outwards. Said shell can form a vesicle lumen.
- compositions of the invention comprise a builder system.
- the builder system is a phosphate-free builder system, as the composition is free of phosphates.
- the composition comprises phosphonates. Accordingly, the term "phosphate-free", as used herein does not include phosphonates.
- the phosphonates included in the builder system are preferably phosphonates based on hydroxyl alkanes, amino alkanes or amino acids, such as 1-hydroxyethane-1 , 1-diphosphonate (HEDP), ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP), and lysine tetramethylene phosphonate (LTMP).
- HEDP 1-diphosphonate
- ETMP ethylenediamine tetramethylene phosphonate
- DTPMP diethylenetriamine pentamethylene phosphonate
- LTMP lysine tetramethylene phosphonate
- phosphonates that are readily water-soluble, in particular lysine tetramethylene phosphonate.
- Water-soluble as used herein, relates to a solubility in water at 20Ā°C of at least 1 g/L, preferably at least 10 g /L.
- Phosphonates are used in amounts of 0.5 to 5.0 wt.%, preferably 2.0 to 3.0 wt.%.
- Suitable inorganic builders include, without limitation, silicates, aluminosilicates (particularly zeolite), and carbonates, with water-soluble inorganic builders and in particular carbonates being preferred.
- Suitable carbonates include alkali metal carbonates, hydrogen carbonates and sesquicarbonates, with alkali metal carbonates, in particular sodium carbonate being preferred.
- inorganic builders in particular water-soluble inorganic builders, preferably carbonates, are used in amounts of up to 8 wt.%, preferably up to 5 wt.% relative to the total weight of the composition.
- carbonate, preferably sodium carbonate is used in amounts of 1.0 to 8.0 wt.%, preferably 3.0 to 5.0 wt.%.
- Suitable polycarboxylic acids which can be used as free acids or in form of their salts, include, but are not limited to, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartric acid, maleic acid, fumaric acid, and sugar acids.
- the free acids can also be used for pH control.
- Preferred are citric acid, succinic acid, glutaric acid, adipic acid and gluconic acid, and combinations thereof.
- citric acid and their salts i.e. citrates.
- the polycarboxylic acids in particular citric acid/citrate, are contained in the compositions of the invention in amounts of 3.0 to 15.0 wt.%, preferably 6.0 to 10.0 wt.%.
- Suitable aminocarboxylic acids or salts thereof are selected from the group consisting of L-glutamic acid ā , ā -diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine ā , ā '-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine ā , ā -diacetic acid, hydroxyethylenediamine triacetic acid (HEDTA), and salts, preferably alkali metal salts thereof as well as combinations of any one of more of the aforementioned. Particularly preferred is GLDA tetrasodium salt.
- the aminocarboxylates are preferably used in amounts of 2.0 to 10.0 wt.%, preferably 3.0 to 5.0 wt.% relative to the total weight of the composition.
- the fifth builder component are acrylate-containing water-soluble polymers, such as alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight Mw in the range of 600 to 750,000 g / mol, as determined by gel permeation chromatography (GPC) according to DIN 55672-1 :2007-08 with THF as an eluent.
- acrylate-containing water-soluble polymers such as alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight Mw in the range of 600 to 750,000 g / mol, as determined by gel permeation chromatography (GPC) according to DIN 55672-1 :2007-08 with THF as an eluent.
- Preferred polymers are polyacrylates with a molecular weight M w of 1 ,000 to 15,000 g / mol, more preferred, due to their solubility, are short-chain polyacrylates with a molecular weight M w of 1 ,000 to 10,000 g / mol, most preferred from 1 ,000 to 5,000 g / mol.
- copolymers of acrylates in particular those of acrylic acid and methacrylic acid, and acrylic acid or methacrylic acid and maleic acid.
- such copolymers can also contain monomers of allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid.
- Preferred acrylates for use in the present invention are alkali metal salts of polymers of acrylic acid, preferably the sodium salts, in particular those with molecular weights in the range of 1 ,000 to 10,000 g / mol or 1 ,000 to 5,000 g / mol.
- Suitable acrylates are commercially available, for example under the tradename Acusol Ā® from Dow Chemical, preferred is, for example, Acusol Ā® 420N.
- the builder system comprises relative to the total weight of the detergent composition:
- (a1 ) 1.0 to 8.0 wt.-%, preferably 3.0 to 5.0 wt.-% of the at least one inorganic builder, preferably a carbonate, more preferably sodium carbonate;
- GLDA L-glutamic acid ā
- HEDTA hydroxyethylenediamine triacetic acid
- alkali metal salts thereof more preferably GLDA tetrasodium salt
- organic builders include polyacetals, dextrins and others. It is however preferred that the compositions are free of these other types of organic builders.
- the builder system is comprised in the compositions in an amount of 10.0 to 30.0 wt.%, preferably 15.0 to 25.0 wt.%.
- the detergent compositions of the invention further comprise a surfactant system.
- Said surfactant system preferably comprises at least one alkyl ether sulfate.
- Preferred alkyl ether sulfates are those of formula (I)
- R represents a linear or branched, substituted or unsubstituted alkyl group, preferably a linear, unsubstituted alkyl group, more preferably a fatty alcohol moiety.
- Preferred R moieties are selected from the group consisting of decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl moieties and mixtures thereof, wherein those groups with an even number of carbon atoms are preferred.
- R moieties are derived from C10-C18 fatty alcohols, such as those derived from coconut oil alcohols, tallow fatty alcohols, lauryl, myristyl, cetyl or stearyl alcohol or from Cio-C2o oxoalcohols.
- AO represents an ethyleneoxide (EO) or propyleneoxide (PO) group, preferably an ethyleneoxide group.
- the index n represents an integer from 1 to 50, preferably from 1 to 20 and more preferably from 1 to 10. Particularly preferably, n is 1 , 2, 3, 4, 5, 6, 7 or 8.
- X represents a monovalent cation or the n-th part of an n-valent cation, preferred are alkali metal cations, specifically Na + and K + , most preferably Na + . Further cations X + may be selected from NH 4 + , 1 ā 2 Zn 2+ ,1 ā 2 Mg 2+ ,1 ā 2 Ca 2+ ,1 ā 2 Mn 2+ , and combinations thereof.
- the detergent compositions comprise an alkyl ether sulfate selected from fatty alcohol ether sulfates of formula (II)
- Particularly preferred lauryl ether sulfate sodium salt with 2 EO, as it is particularly advantageous for achieving the desired viscosity ranges.
- the level of ethoxylation is an average value and can, for a specific compound, be an integer or fractional number.
- the alkyl ether sulfate is preferably contained in the compositions of the invention in an amount of 2.0 to 8.0 wt.% relative to the total weight of the composition, preferably 3.0 to 7.0 wt.%.
- the surfactant system comprises at least one alkyl benzene sulfonate.
- Said alkyl benzene sulfonate may be present alternatively to the above alkyl ether sulfate or, preferably, in addition to it.
- alkyl benzene sulfonates include, but are not limited to linear and branched alkyl benzene sulfonates, preferably linear alkyl benzene sulfonates.
- Exemplary compounds are those of formula (III)
- R ' and R " are independently H or alkyl and combined comprise 9 to 19, preferably 9 to 15 and more preferably 9 to 13 carbon atoms.
- Particularly preferred are dodecyl and tridecyl benzene sulfonates, in particular the sodium salts thereof.
- Preferred contents of the alkyl benzene sulfonates range from 3.0 to 22.0 wt.%, preferably 10.0 to 15.0 wt.%, relative to the total weight of the composition.
- compositions of the invention may further comprise one or more nonionic surfactants.
- Preferred nonionic surfactants are those of formula (IV)
- R 2 represents a linear or branched substituted or unsubstituted alkyl moiety
- AO represents an ethylene oxide (EO) or propylene oxide (PO) group
- m is an integer from 1 to 50.
- R 2 preferably represents a linear or branched, substituted or unsubstited alkyl group, preferably a linear, unsubstituted alkyl group, particularly preferred a fatty alcohol group.
- Preferred groups are R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl groups and combinations thereof, wherein those groups with an even number of carbon atoms are preferred.
- R 2 groups derived from C12-C18 fatty alcohols such as coconut oil alcohol, tallow oil alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C10-C20 oxoalcohols.
- AO represents an ethyleneoxide (EO) or propyleneoxide (PO) group, preferably an ethyleneoxide group.
- the index m represents an integer from 1 to 50, preferably from 1 to 20 and more preferably from 1 to 6. Particularly preferably, m is 1 , 2, 3, 4 or 5, most preferably 3-5, as higher degrees of ethoxylation may negatively influence viscosity and stability.
- the detergent compositions comprise an alkyl ether selected from fatty alcohol ethers of formula (V)
- Such nonionic alkyl ethers may be contained in the formulation in amounts of 0.0 to 5.0 wt.%, preferably 2.0 to 3.0 wt.%.
- the detergents may further include other nonionic surfactants, such as alkyl glucosides of the general formula RO(G)x, where R is a primary linear or 2-methyl-branched aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G stands for a glucose unit.
- R is a primary linear or 2-methyl-branched aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G stands for a glucose unit.
- the degree of oligomerization x which indicates the distribution of monoglucosides and oligoglucosides, is a number of 1 to 10 and preferably a number of 1.2 to 1 .4. However, in preferred embodiments, the compositions do not include such alkyl glucosides.
- the surfactant system comprises at least two anionic surfactants, namely at least one alkyl ether sulfate and preferably at least one alkyl benzene sulfonate, and optionally an alkyl ether.
- compositions may comprise, for example, 5.0 to 25.0, preferably 13.0 to 20.0 wt.% of the surfactant system.
- Said surfactant system may comprise or consist of anionic surfactants, preferably (1 ) 2.0 to 8.0 wt.%, preferably 3.0 to 7.0 wt.% C10-16 alkyl ether sulfates with 1 to 7 EO, preferably C12-14 fatty alcohol ether sulfates with 1-3 EO, more preferably lauryl ether sulfate with 2 EO; (2) 3.0 to 22.0, preferably 10.0 to 15.0 wt.%, of a linear alkyl benzene sulfonate, preferably dodecyl or tridecyl benzene sulfonate; and (3) 0.0 to 5.0 wt.%, preferably 2.0 to 3.0 wt.%, C12-18 alkyl ethers with 1-6 EO, preferably C12-14 alkyl ethers having 1-5
- the detergent compositions of the invention are aqueous liquid compositions and as such comprise significant quantities of water, typically 35.0 to 85.0 wt.%, preferably 50.0 to 70.0 wt.%.
- the pH value of the detergents according to the invention is generally in the range of from pH 9 to 12, preferably in the range from 10.0 to 1 1.0. Relatively high pH values, for example above 9, may be adjusted by the use of small quantities of sodium hydroxide or alkaline salts, such as sodium carbonate.
- the liquid detergents are typically opaque, are flowable, and may be poured under the sole effect of gravity without any need for other shear forces to be applied. Their viscosity is generally greater than 1 ,000 mPas (Brookfield viscosimeter, spindle 3, 12 rpm, 20Ā° C), namely in the range of between 1 ,000 and 10,000 mPas, preferably between 2,000 and 6,000 mPas.
- compositions may further comprises stabilizers and/or rheology modifiers (thickeners), preferably both.
- stabilizers and/or rheology modifiers are typically polymers, such as polymers based on acrylates or methacrylates.
- suitable acrylate polymers comprise, but are not limited to, polymers of the AcusolĀ® series (Dow Chemicals, Midland, USA), AlcosperseĀ® series, AquatreatĀ® series (both Akzo Nobel, Amsterdam, The Netherlands), Good- riteĀ® series (Emerald Performance Materials, Cuyahoga Falls, USA), JunlonĀ® series, JurymerĀ® series, RheogicĀ® series, AranĀ® series (all Toagosei Co., Ltd., Tokyo, Japan), GlascolĀ® series (BASF, Ludwigshafen, Germany), AqualicĀ® series (Nippon Shokubai Co., Ltd., Osaka, Japan), CarbopolĀ® series and CarbosetĀ® series (both The Lubrizol Corporation, Wickliffe, USA).
- the detergents may commonly contain at least one, preferably two or more other substances selected from the group consisting of soaps, pH adjusting agents, perfumes, fluorescing agents (optical brighteners), dyes, colorants, antimicrobial active substances, germicides, fungicides, antioxidants, preservatives, and softening compounds.
- ingredients include silicone oils, anti-redeposition agents, anti-greying agents, shrinkage preventers, wrinkle protection agents, dye transfer inhibitors, corrosion inhibitors, antistatic agents, bittering agents, ironing adjuvants, proofing and impregnation agents, swelling and anti-slip agents, complexing agents and UV absorbers.
- bleaching agents may be bleaching agents, bleach activators, bleach catalysts, and enzymes, however, in various embodiments, the compositions are free of those.
- the detergent compositions further comprise relative to their total weight 0.25 to 15 wt.%, preferably 0.5 to 12.5 wt.%, preferably 2.0 to 6.0 wt.% soaps.
- ingredients that are commonly used include colorants, perfumes and optical brighteners, as well as pH adjusting agents. All of these ingredients are well-known in the art and readily available.
- the present invention further relates to methods for cleaning textiles, wherein a washing liquor containing the liquid detergent composition of the present invention contacts the textile in at least one method step.
- the methods are preferably carried out in an automatic washing machine.
- Methods for cleaning of textiles are generally characterized by the fact that in several different process steps various cleaning-active substances are applied to the textiles and after the contact time said cleaning-active substances are washed off, or that the textiles are treated in any other way with a detergent or a solution of said substance.
- Also encompassed by the present invention is the use of the builder compositions disclosed herein for providing builder properties to aqueous, phosphate-free, structured liquid detergent compositions.
- Washed swatches are read using a Hunter Lab Reflectometer thereby the Lightness (L * ) is recorded.
- the resultant L * value for washed stains can be compared to estimate wash performance.
- the criteria of +/-1 can be applied for top load wash performance.
- a snap-shot of overall performance can be made by comparing the total L * score for all 13 technical stains and applying the following criteria:
- Example 1 Sodium carbonate built HDL
- Example L is an efficient replacement for the phosphate builder. It does have a higher surfactant dose per wash but the builder dose per wash is significantly lower.
- Citric acid monohydrate 0.00 2.84 0.00 2.84 2.84 2.84 2.84
- M and N show a very significant performance effect due to citrate and carbonate while O, P and Q show smaller but still significant effects due to Phosphonate, Polyacrylate and GLDA.
- Formula "% m/mā is the concentration of each raw material based on 100% active ingredient.
Abstract
An aqueous, phosphate-free, structured heavy duty liquid detergent composition comprising a surfactant system, a builder system and water, wherein the builder system comprises (A) at least one inorganic builder (sodium carbonate); (B) at least one polycarboxylic acid or salt thereof (citric acid); (C) at least one aminocarboxylate (GLDA tetrasodium salt); (D) at least one phosphonate (lysine tetra methylene phosphonate (LTMP)); and (E) at least one acrylate-containing water-soluble polymer or acid derivative or salts thereof (sodium salt of an acrylic acid copolymer). Method for cleaning textiles, wherein a washing liquor containing the detergent composition contacts the textile in at least one method step. Use of the detergent composition.
Description
"Penta-Built Liquid Detergent Composition"
The present invention relates to an aqueous, phosphate-free, structured liquid detergent composition, in particular a heavy duty liquid detergent (HDL) that comprises a builder system, a surfactant system and water, wherein the builder system comprises five separate builder components. The invention further relates to methods for washing of textiles using the detergents of the invention.
Liquid detergent compositions are well-known in the art and widely used. Over recent years, the have become more and more popular with the consumers because they offer a number of advantages over solid compositions, including, for example, the ease of dosing, dispensing and dissolving into a laundering liquor. In addition, they are perceived to be safer and less harsh to the textiles and environment compared to solid compositions. In particular for laundering colored fabrics they have gained popularity ever since their introduction on the market.
Recently, for environmental and regulatory reasons the demand for phosphate-free liquid detergents has increased. However, liquid detergent compositions, in particular phosphate-free heavy duty liquid (HDL) detergents suffer from physical and chemical instability and viscosity problems. This is particularly problematic for highly concentrated formulations. While HDL detergents have been introduced as early as the 1970's, the known stable formulations rely on the use of phosphates, in particular sodium tripolyphosphate (STPP), to form structured liquids containing high levels of builders and surfactants. In these built HDLs multilayered vesicles are formed that stabilize the formulation and prevent precipitation of the anionic surfactants by the builder components. These structures are stable and can be characterized by microscopic examination under polarized light and conductivity measurements. STPP was particularly suited to formation of vesicles with sodium alkylbenzene sulfonate (sodium LAS). In addition, STPP was well established as a builder in detergent powders and acts as a chelating agent, inhibits soil re- deposition during the wash and boosts overall detergency. The result of the use of STPP was the development of high performance and low cost HDL. However, as mentioned above, environmental concerns over the use of phosphates, including STPP, in laundry detergents have resulted in phosphate use being banned in some countries and a negative public image in most developed markets. While alternatives to STPP, such as zeolite, sodium citrate, and sodium carbonate, are known, these show poor performance relative to phosphate built HDL.
Therefore, there is still need in the art for phosphate-free, structured HDL detergents that have comparable performance as the previously used phosphate-based formulations. Accordingly, it is an object of the present invention to meet this need by providing an aqueous, phosphate-free,
structured liquid detergent composition, in particular a HDL detergent that exhibits the desired performance.
It has surprisingly been found by the inventors that this object can be met by a composition that comprises a specific builder system, a surfactant system and water. It has been demonstrated that such a detergent shares a similar washing performance as the previously used STPP-containing compositions.
In a first aspect, the present invention therefore relates to an aqueous, phosphate-free, structured liquid detergent composition comprising a surfactant system, a builder system and water, wherein the builder system comprises
(A) at least one inorganic builder, preferably a carbonate, more preferably sodium
carbonate;
(B) at least one polycarboxylic acid or salt thereof, preferably a hydroxyl group-containing polycarboxylic acid or salt thereof, more preferably citric acid or citrate;
(C) at least one aminocarboxylate, preferably selected from the group consisting of L- glutamic acid Ī,Ī-diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine Ī,Ī'-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine Ī,Ī-diacetic acid, hydroxyethylenediamine triacetic acid (HEDTA), and alkali metal salts thereof, more preferably GLDA tetrasodium salt;
(D) at least one phosphonate, preferably lysine tetra methylene phosphonate (LTMP); and
(E) at least one acrylate-containing water-soluble polymer or acid derivative or salts
thereof, preferably a sodium salt of an acrylic acid copolymer.
In a further aspect, the invention relates to methods for cleaning textiles, wherein a washing liquor containing the liquid detergent composition of the present invention contacts the textile in at least one method step.
In still another aspect, the invention also encompasses the use of a composition comprising
(A) at least one inorganic builder, preferably a carbonate, more preferably sodium
carbonate;
(B) at least one polycarboxylic acid or salt thereof, preferably a hydroxyl group-containing polycarboxylic acid or salt thereof, more preferably citric acid or citrate;
(C) at least one aminocarboxylate, preferably selected from the group consisting of L- glutamic acid Ī,Ī-diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine Ī,Ī'-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine Ī,Ī-diacetic acid, hydroxyethylenediamine
triacetic acid (HEDTA), and alkali metal salts thereof, more preferably GLDA tetrasodium salt;
(D) at least one phosphonate, preferably lysine tetra methylene phosphonate (LTMP); and
(E) at least one acrylate-containing water-soluble polymer or acid derivative or salts thereof, preferably a sodium salt of an acrylic acid copolymer,
as a builder system in an aqueous, phosphate-free, structured liquid detergent composition.
"At least one", as used herein, relates to one or more, i.e. 1 , 2, 3, 4, 5, 6, 7, 8, 9, or more. If used in combination with a compound, the term does not relate to the absolute number of molecules but rather to the number of different types of said compound. "At least one inorganic builder" thus means that at least one type but that also 2 or more different inorganic builder types can be present.
If not indicated otherwise, all viscosities referred to herein are viscosities measured at 20Ā°C by a Brookfield LVT, Spindle No. 3 at 12 rpm.
If not indicated otherwise, all percentages are by weight relative to the total weight of the composition.
"Free of", as used herein in relation to a specific type of component, means that the referenced composition does not contain more than 0.5 wt.%, preferably no more than 0.1 wt.%, more preferably no more than 0.05 wt.% of said component relative to the total weight of the composition. Most preferably, said component is not contained at all.
The detergent compositions of the present invention can be used as detergents for textiles, carpets or natural fibers. In preferred embodiments, the detergents disclosed herein are heavy duty liquid (HDL) detergents.
The present invention is based on the inventors' surprising finding, that by use of the disclosed builder system structured liquid detergent compositions may be formed that have the desired washing performance.
"Washing performance", as used herein, relates to the removal of stains, in particular stains sensitive to surfactants. The removal can be evaluated by measuring a brightening of the stain either instrumentally or by visual inspection.
Structured liquids are widely used in the field of detergents. They can either be internally structured by one or more of the primary ingredients, such as the surfactants, and/or by using secondary
additives, such as certain polymers and/or silicates. Structuring is used to endow the composition with properties such as a turbid appearance or certain flow properties. Such structured liquids may also contain suspended solids. While structured liquids provide more formulation flexibility compared to isotropic liquids, they often suffer from stability and viscosity problems. The presently disclosed formulations, however, provide for compositions that have the desired viscosities while at the same time showing good stability.
In various embodiments, the liquid detergent compositions of the invention are internally structured in that the surfactant system leads to formation of multilayered vesicles. "Structured", as used herein, therefore means that the compositions are preferably internally structured by formation of multilayered vesicles. "Multilayered vesicles" preferably relates to essentially spherical vesicles that have a multilayered, typically double-layered, shell formed of molecules comprising hydrophobic moieties, with said hydrophobic moieties arranged such that they face each other while the more hydrophilic parts of the molecules face outwards. Said shell can form a vesicle lumen.
The compositions of the invention comprise a builder system. The builder system is a phosphate- free builder system, as the composition is free of phosphates. However, the composition comprises phosphonates. Accordingly, the term "phosphate-free", as used herein does not include phosphonates.
The phosphonates included in the builder system are preferably phosphonates based on hydroxyl alkanes, amino alkanes or amino acids, such as 1-hydroxyethane-1 , 1-diphosphonate (HEDP), ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP), and lysine tetramethylene phosphonate (LTMP). Preferred are
phosphonates that are readily water-soluble, in particular lysine tetramethylene phosphonate.
"Water-soluble", as used herein, relates to a solubility in water at 20Ā°C of at least 1 g/L, preferably at least 10 g /L.
Phosphonates are used in amounts of 0.5 to 5.0 wt.%, preferably 2.0 to 3.0 wt.%.
Suitable inorganic builders include, without limitation, silicates, aluminosilicates (particularly zeolite), and carbonates, with water-soluble inorganic builders and in particular carbonates being preferred.
Suitable carbonates include alkali metal carbonates, hydrogen carbonates and sesquicarbonates, with alkali metal carbonates, in particular sodium carbonate being preferred.
In various embodiments, inorganic builders, in particular water-soluble inorganic builders, preferably carbonates, are used in amounts of up to 8 wt.%, preferably up to 5 wt.% relative to the total weight of the composition. In preferred embodiments, carbonate, preferably sodium carbonate, is used in amounts of 1.0 to 8.0 wt.%, preferably 3.0 to 5.0 wt.%.
Suitable polycarboxylic acids, which can be used as free acids or in form of their salts, include, but are not limited to, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartric acid, maleic acid, fumaric acid, and sugar acids. In addition to their builder properties, the free acids can also be used for pH control. Preferred are citric acid, succinic acid, glutaric acid, adipic acid and gluconic acid, and combinations thereof.
Particularly preferred are citric acid and their salts, i.e. citrates. In various embodiments, the polycarboxylic acids, in particular citric acid/citrate, are contained in the compositions of the invention in amounts of 3.0 to 15.0 wt.%, preferably 6.0 to 10.0 wt.%.
Suitable aminocarboxylic acids or salts thereof, i.e. aminocarboxylates, are selected from the group consisting of L-glutamic acid Ī,Ī-diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine Ī,Ī'-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine Ī,Ī-diacetic acid, hydroxyethylenediamine triacetic acid (HEDTA), and salts, preferably alkali metal salts thereof as well as combinations of any one of more of the aforementioned. Particularly preferred is GLDA tetrasodium salt.
The aminocarboxylates are preferably used in amounts of 2.0 to 10.0 wt.%, preferably 3.0 to 5.0 wt.% relative to the total weight of the composition.
Finally, the fifth builder component are acrylate-containing water-soluble polymers, such as alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight Mw in the range of 600 to 750,000 g / mol, as determined by gel permeation chromatography (GPC) according to DIN 55672-1 :2007-08 with THF as an eluent.
Preferred polymers are polyacrylates with a molecular weight Mw of 1 ,000 to 15,000 g / mol, more preferred, due to their solubility, are short-chain polyacrylates with a molecular weight Mw of 1 ,000 to 10,000 g / mol, most preferred from 1 ,000 to 5,000 g / mol.
Also suitable are copolymers of acrylates, in particular those of acrylic acid and methacrylic acid, and acrylic acid or methacrylic acid and maleic acid. To further improve solubility, such copolymers can also contain monomers of allyl sulfonic acids, such as allyloxybenzene sulfonic acid and methallyl sulfonic acid.
Preferred acrylates for use in the present invention are alkali metal salts of polymers of acrylic acid, preferably the sodium salts, in particular those with molecular weights in the range of 1 ,000 to 10,000 g / mol or 1 ,000 to 5,000 g / mol. Suitable acrylates are commercially available, for example under the tradename AcusolĀ® from Dow Chemical, preferred is, for example, AcusolĀ® 420N.
In various embodiments, the builder system comprises relative to the total weight of the detergent composition:
(a1 ) 1.0 to 8.0 wt.-%, preferably 3.0 to 5.0 wt.-% of the at least one inorganic builder, preferably a carbonate, more preferably sodium carbonate;
(a2) 3.0 to 15.0 wt.-%, preferably 6.0 to 10.0 wt.-% of the at least one polycarboxylic acid or salt thereof, preferably a hydroxyl group-containing polycarboxylic acid or salt thereof, more preferably citric acid or citrate, most preferably preferably sodium citrate;
(a3) 2.0 to 10.0 wt.-%, preferably 3.0 to 5.0 wt.-% of the at least one aminocarboxylate, preferably selected from the group consisting of L-glutamic acid Ī,Ī-diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine Ī,Ī'-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine Ī,Ī-diacetic acid,
hydroxyethylenediamine triacetic acid (HEDTA), and alkali metal salts thereof, more preferably GLDA tetrasodium salt;
(a4) 0.5 to 5.0 wt.%, preferably 2.0 to 3.0 wt.-% of the at least one phosphonate, preferably lysine tetra methylene phosphonate (LTMP); and
(a5) 0.5 to 5.0 wt.%, preferably 1.0 to 2.0 wt.% of the at least one acrylate-containing water-soluble polymer or acid derivative or salts thereof, preferably a sodium salt of an acrylic acid copolymer.
Further organic builders include polyacetals, dextrins and others. It is however preferred that the compositions are free of these other types of organic builders.
In various embodiments, the builder system is comprised in the compositions in an amount of 10.0 to 30.0 wt.%, preferably 15.0 to 25.0 wt.%.
The detergent compositions of the invention further comprise a surfactant system. Said surfactant system preferably comprises at least one alkyl ether sulfate. Preferred alkyl ether sulfates are those of formula (I)
R -0-(AO)n-S03- X+ (I).
In formula (I) R represents a linear or branched, substituted or unsubstituted alkyl group, preferably a linear, unsubstituted alkyl group, more preferably a fatty alcohol moiety. Preferred R moieties are selected from the group consisting of decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl moieties and mixtures thereof,
wherein those groups with an even number of carbon atoms are preferred. Particularly preferred R moieties are derived from C10-C18 fatty alcohols, such as those derived from coconut oil alcohols, tallow fatty alcohols, lauryl, myristyl, cetyl or stearyl alcohol or from Cio-C2o oxoalcohols.
AO represents an ethyleneoxide (EO) or propyleneoxide (PO) group, preferably an ethyleneoxide group. The index n represents an integer from 1 to 50, preferably from 1 to 20 and more preferably from 1 to 10. Particularly preferably, n is 1 , 2, 3, 4, 5, 6, 7 or 8. X represents a monovalent cation or the n-th part of an n-valent cation, preferred are alkali metal cations, specifically Na+ and K+, most preferably Na+. Further cations X+ may be selected from NH4 +, Ā½ Zn2+,Ā½ Mg2+,Ā½ Ca2+,Ā½ Mn2+, and combinations thereof.
In various preferred embodiments, the detergent compositions comprise an alkyl ether sulfate selected from fatty alcohol ether sulfates of formula (II)
wherein k = 9 to 19, and n = 1 , 2, 3, 4, 5, 6, 7 or 8. Preferred are C10-16 fatty alcohol ether sulfates with 1-7, more preferably 1-3 EO (k = 9-15, n = 1-7, 1 -3), even more preferred the C12-14 fatty alcohol ether sulfates with 1 -3, particularly 2 EO (k = 1 1-13, n = 1-3 or 2), more particularly the sodium salts thereof. Particularly preferred is lauryl ether sulfate sodium salt with 2 EO, as it is particularly advantageous for achieving the desired viscosity ranges. The level of ethoxylation is an average value and can, for a specific compound, be an integer or fractional number.
The alkyl ether sulfate is preferably contained in the compositions of the invention in an amount of 2.0 to 8.0 wt.% relative to the total weight of the composition, preferably 3.0 to 7.0 wt.%.
In various embodiments, the surfactant system comprises at least one alkyl benzene sulfonate. Said alkyl benzene sulfonate may be present alternatively to the above alkyl ether sulfate or, preferably, in addition to it.
Exemplary alkyl benzene sulfonates include, but are not limited to linear and branched alkyl benzene sulfonates, preferably linear alkyl benzene sulfonates. Exemplary compounds are those of formula (III)
wherein R' and R" are independently H or alkyl and combined comprise 9 to 19, preferably 9 to 15 and more preferably 9 to 13 carbon atoms. Particularly preferred are dodecyl and tridecyl benzene
sulfonates, in particular the sodium salts thereof. Preferred contents of the alkyl benzene sulfonates range from 3.0 to 22.0 wt.%, preferably 10.0 to 15.0 wt.%, relative to the total weight of the composition.
In addition, the compositions of the invention may further comprise one or more nonionic surfactants. Preferred nonionic surfactants are those of formula (IV)
wherein R2 represents a linear or branched substituted or unsubstituted alkyl moiety, AO represents an ethylene oxide (EO) or propylene oxide (PO) group and m is an integer from 1 to 50.
In formula (IV) R2 preferably represents a linear or branched, substituted or unsubstited alkyl group, preferably a linear, unsubstituted alkyl group, particularly preferred a fatty alcohol group. Preferred groups are R2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl groups and combinations thereof, wherein those groups with an even number of carbon atoms are preferred. Particularly preferred are R2 groups derived from C12-C18 fatty alcohols, such as coconut oil alcohol, tallow oil alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C10-C20 oxoalcohols.
AO represents an ethyleneoxide (EO) or propyleneoxide (PO) group, preferably an ethyleneoxide group. The index m represents an integer from 1 to 50, preferably from 1 to 20 and more preferably from 1 to 6. Particularly preferably, m is 1 , 2, 3, 4 or 5, most preferably 3-5, as higher degrees of ethoxylation may negatively influence viscosity and stability.
In various preferred embodiments, the detergent compositions comprise an alkyl ether selected from fatty alcohol ethers of formula (V)
wherein k = 1 1 to 19, m = 1 , 2, 3, 4, 5, 6, 7 or 8. Preferred are C12-18 fatty alcohols with 1-6 EO (k = 1 1-17, m = 1 -5 in formula (V)). More preferred are C12-14 alcohols having 1-5 EO, most preferred are C12-14 alkyl ethers with 3-5 EO, in particular lauryl ether with 5 EO.
Such nonionic alkyl ethers may be contained in the formulation in amounts of 0.0 to 5.0 wt.%, preferably 2.0 to 3.0 wt.%.
The detergents may further include other nonionic surfactants, such as alkyl glucosides of the general formula RO(G)x, where R is a primary linear or 2-methyl-branched aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G stands for a glucose unit. The degree of oligomerization x, which indicates the distribution of monoglucosides and
oligoglucosides, is a number of 1 to 10 and preferably a number of 1.2 to 1 .4. However, in preferred embodiments, the compositions do not include such alkyl glucosides.
In various embodiments, the surfactant system comprises at least two anionic surfactants, namely at least one alkyl ether sulfate and preferably at least one alkyl benzene sulfonate, and optionally an alkyl ether.
The compositions may comprise, for example, 5.0 to 25.0, preferably 13.0 to 20.0 wt.% of the surfactant system. Said surfactant system may comprise or consist of anionic surfactants, preferably (1 ) 2.0 to 8.0 wt.%, preferably 3.0 to 7.0 wt.% C10-16 alkyl ether sulfates with 1 to 7 EO, preferably C12-14 fatty alcohol ether sulfates with 1-3 EO, more preferably lauryl ether sulfate with 2 EO; (2) 3.0 to 22.0, preferably 10.0 to 15.0 wt.%, of a linear alkyl benzene sulfonate, preferably dodecyl or tridecyl benzene sulfonate; and (3) 0.0 to 5.0 wt.%, preferably 2.0 to 3.0 wt.%, C12-18 alkyl ethers with 1-6 EO, preferably C12-14 alkyl ethers having 1-5 EO, most preferably lauryl ether with 5 EO. All afore-mentioned percentages relate to the total weight of the composition.
The detergent compositions of the invention are aqueous liquid compositions and as such comprise significant quantities of water, typically 35.0 to 85.0 wt.%, preferably 50.0 to 70.0 wt.%.
The pH value of the detergents according to the invention is generally in the range of from pH 9 to 12, preferably in the range from 10.0 to 1 1.0. Relatively high pH values, for example above 9, may be adjusted by the use of small quantities of sodium hydroxide or alkaline salts, such as sodium carbonate. The liquid detergents are typically opaque, are flowable, and may be poured under the sole effect of gravity without any need for other shear forces to be applied. Their viscosity is generally greater than 1 ,000 mPas (Brookfield viscosimeter, spindle 3, 12 rpm, 20Ā° C), namely in the range of between 1 ,000 and 10,000 mPas, preferably between 2,000 and 6,000 mPas.
To ensure stability and the desired viscosity, the compositions may further comprises stabilizers and/or rheology modifiers (thickeners), preferably both. These compounds are typically polymers, such as polymers based on acrylates or methacrylates. Examples of suitable acrylate polymers comprise, but are not limited to, polymers of the AcusolĀ® series (Dow Chemicals, Midland, USA), AlcosperseĀ® series, AquatreatĀ® series (both Akzo Nobel, Amsterdam, The Netherlands), Good- riteĀ® series (Emerald Performance Materials, Cuyahoga Falls, USA), JunlonĀ® series, JurymerĀ® series, RheogicĀ® series, AranĀ® series (all Toagosei Co., Ltd., Tokyo, Japan), GlascolĀ® series (BASF, Ludwigshafen, Germany), AqualicĀ® series (Nippon Shokubai Co., Ltd., Osaka, Japan), CarbopolĀ® series and CarbosetĀ® series (both The Lubrizol Corporation, Wickliffe, USA). Preferred are, for example, AlcosperseĀ® 325 (Akzo nobel), as a stabilizer, and AcusolĀ® 810 (Dow Chemical), as a thickener. These components are typically used in amounts of up to 1 wt.%, typically 0,1 to 0.5 wt.%.
In addition to the ingredients mentioned above, however, the detergents may commonly contain at least one, preferably two or more other substances selected from the group consisting of soaps, pH adjusting agents, perfumes, fluorescing agents (optical brighteners), dyes, colorants, antimicrobial active substances, germicides, fungicides, antioxidants, preservatives, and softening compounds.
Further possible ingredients include silicone oils, anti-redeposition agents, anti-greying agents, shrinkage preventers, wrinkle protection agents, dye transfer inhibitors, corrosion inhibitors, antistatic agents, bittering agents, ironing adjuvants, proofing and impregnation agents, swelling and anti-slip agents, complexing agents and UV absorbers.
Also included may be bleaching agents, bleach activators, bleach catalysts, and enzymes, however, in various embodiments, the compositions are free of those.
For cold wash properties, it can be beneficial to additionally include soaps. Accordingly, in some embodiments, the detergent compositions further comprise relative to their total weight 0.25 to 15 wt.%, preferably 0.5 to 12.5 wt.%, preferably 2.0 to 6.0 wt.% soaps. Preferred are soaps from C12- C18 fatty acids, i.e. the salts of lauric acid, myristic acid, palmitic acid, stearic acid, or mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil, or tallow fatty acids.
Further ingredients that are commonly used include colorants, perfumes and optical brighteners, as well as pH adjusting agents. All of these ingredients are well-known in the art and readily available.
The present invention further relates to methods for cleaning textiles, wherein a washing liquor containing the liquid detergent composition of the present invention contacts the textile in at least one method step. The methods are preferably carried out in an automatic washing machine.
Methods for cleaning of textiles are generally characterized by the fact that in several different process steps various cleaning-active substances are applied to the textiles and after the contact time said cleaning-active substances are washed off, or that the textiles are treated in any other way with a detergent or a solution of said substance.
Also encompassed by the present invention is the use of the builder compositions disclosed herein for providing builder properties to aqueous, phosphate-free, structured liquid detergent compositions.
All embodiments described herein in relation to the compositions of the invention are similarly applicable to the methods and uses of the invention and vice versa.
Examples
Example 1 :
Wash performance testing was conducted in top load domestic washing machines under the following conditions:
Table 1 : Wash conditions
Table 2: Technical stain
Measurement of soil removal
Washed swatches are read using a Hunter Lab Reflectometer thereby the Lightness (L*) is recorded. The reflectometer is standardized with black (L* = 0) and white (L* = 100) standards. The
resultant L* value for washed stains can be compared to estimate wash performance.
Measurements are in triplicate and student t-test is applied at a 95% confidence interval. For individual stains the following criteria is applied:
Statistically better: Test statistic > 2.67 and delta L* >1
Statistically worse: Test statistic <-2.67 and delta L* <-1
In general, the criteria of +/-1 can be applied for top load wash performance.
A snap-shot of overall performance can be made by comparing the total L* score for all 13 technical stains and applying the following criteria:
Top load: >5L* is statistically better and <-5L* is statistically worse. However, L* scores for individual stains must be evaluated to obtain an accurate estimation of performance.
In all wash studies the phosphate-based formula was used as a benchmark and in Table 3 is used as a reference.
Example 1 : Sodium carbonate built HDL
In this series, sodium tripolyphosphate was removed, the builder sodium carbonate was kept constant, while the surfactant active levels were increased. Tetrasodium GLDA and polyacrylate were included to compensate for the removal of sodium tripolyphosphate. The wash data shows that a simple builder/surfactant combination cannot deliver the same wash performance as the reference phosphate-based detergent.
Table 3: Sodium carbonate built HDL Wash Performance and Composition
Phosphate
Product description A B C D E F
Reference
Delta L* 0 -21 -20 -19 -14.6 -18.5 -9.6
Total surfactant (g/wash) 7.08 5.05 7.57 10.08 12.61 15.13 20.19
Total builder (g/wash) 13.29 4.82 4.82 4.82 4.82 4.82 4.82
Ingredient Composition of formulations (grams/wash)
Deionised Water QS QS QS QS QS QS QS
Sodium LAS 5.37 2.34 3.51 4.67 5.84 7.01 9.35
Sodium laureth-2 sulfate 1.71 1.45 2.17 2.89 3.62 4.34 5.79
Laureth-8 0.00 1.26 1.89 2.52 3.15 3.78 5.05
Sodium Tripolyphosphate 10.43 0.00 0.00 0.00 0.00 0.00 0.00
Soda ash 2.75 3.71 3.71 3.71 3.71 3.71 3.71
Sodium Bicarbonate 0.1 1 0.00 0.00 0.00 0.00 0.00 0.00
Tetrasodium GLDA 0.00 0.37 0.37 0.37 0.37 0.37 0.37
Polyacrylate builder 0.00 0.74 0.74 0.74 0.74 0.74 0.74
Total L* scores relative to the Phosphate reference demonstrate that replacement of phosphate by increasing surfactant active does not compensate for the low in top load wash performance. Increasing the surfactant concentration by almost 3-fold still resulted in lower top load wash performance.
Example 2: Penta-built HDL
Changing the focus from the surfactant to the builder system was carried out and much better top load wash performance wash results were obtained. A system comprising of 5 builders in combination with anionic surfactants alone gave surprising results:
Table 4 - Wash Performance and Composition of Pentabuilt Formulations
In the system comprising of anionic and nonionic surfactants reducing the surfactant concentration resulted in reduced top load wash performance. However, in systems where nonionic surfactants were excluded the wash performance did not reduce as the anionic surfactant concentration was also reduced.
Example L is an efficient replacement for the phosphate builder. It does have a higher surfactant dose per wash but the builder dose per wash is significantly lower.
This correlated with previous testing on phosphate built formulations where the inclusion of nonionic surfactants does not contribute significantly to wash performance in top load machines. Additionally, if this builder system is contributing to performance the same way as a phosphate built system, then there should also be a corresponding loss of wash performance when the builders are reduced.
Example 5: Wash performance effect of builders
Another wash study was conducted to examine the effect of removing individual builders from the formulation.
The results confirm performance found in the previous wash study and show that each builder has a significant effect on the overall wash performance.
Table 5: Wash performance effect of builders
Product description Phosphate L M N O P Q
Reference
Delta L* 0 -2.3 -16.6 -14.8 -5.9 -7.1 -8
Total surfactant (g/wash) 7.08 7.56 7.56 7.56 7.56 7.56 7.56
Total builder (g/wash) 13.29 9.46 5.65 7.57 8.33 8.70 7.57
Ingredient Composition of formulations (grams/wash)
Deionised Water QS QS QS QS QS QS QS
Sodium C13 LAS 5.37 6.05 6.05 6.05 6.05 6.05 6.05
Sodium laureth-2 sulfate 1.71 1.51 1.51 1.51 1 .51 1.51 1.51
Sodium Tripolyphosphate 10.43 0.00 0.00 0.00 0.00 0.00 0.00
Sodium Carbonate 2.75 1.89 1.89 0.00 1 .89 1.89 1.89
Sodium Bicarbonate 0.1 1 0.00 0.00 0.00 0.00 0.00 0.00
Citric acid monohydrate 0.00 2.84 0.00 2.84 2.84 2.84 2.84
Sodium hydroxide 50% 0.00 0.95 0.00 0.95 0.95 0.95 0.95
Tetrasodium GLDA 0.00 1.89 1.88 1.89 1 .89 1.89 0.00
Lysine tetramethylene 0.00 1.13 1.13 1.13 0.00 1.13 1.13 phosphonate
Polyacrylate builder 0.00 0.76 0.75 0.76 0.76 0.00 0.76
Examples M and N show a very significant performance effect due to citrate and carbonate while O, P and Q show smaller but still significant effects due to Phosphonate, Polyacrylate and GLDA.
Formulations
Initial formulation work has been conducted and it was found that a multi-layered vesicle structure could be formed but these were found to be unstable. Addition of a C9 hydrophobically modified polyacrylate, AlcosperseĀ® 325, was required to achieve a stable formulation. Additionally, a polyacrylate thickener such as AcusolĀ® 81 OA, could be incorporated to achieve a more viscous product.
Formulations are summarized in Table 6, which shows that the grams per wash of each raw material are kept constant but the percentage in the formula is adjusted to achieve the required dose.
Table 6: Prototype penta-built HDL formulation
Formula "% m/m" is the concentration of each raw material based on 100% active ingredient.
Claims
1. Aqueous, phosphate-free, structured liquid detergent composition comprising a surfactant system, a builder system and water, wherein the builder system comprises
(A) at least one inorganic builder, preferably a carbonate, more preferably sodium
carbonate;
(B) at least one polycarboxylic acid or salt thereof, preferably a hydroxyl group-containing polycarboxylic acid or salt thereof, more preferably citric acid or citrate;
(C) at least one aminocarboxylate, preferably selected from the group consisting of L- glutamic acid Ī,Ī-diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine Ī,Ī'-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine Ī,Ī-diacetic acid, hydroxyethylenediamine triacetic acid (HEDTA), and alkali metal salts thereof, more preferably GLDA tetrasodium salt;
(D) at least one phosphonate, preferably lysine tetra methylene phosphonate (LTMP); and
(E) at least one acrylate-containing water-soluble polymer or acid derivative or salts
thereof, preferably a sodium salt of an acrylic acid copolymer.
2. The detergent composition according to claim 1 , wherein the composition comprises relative to the total weight of the composition
(a) 10.0 to 30.0 wt.-%, preferably 15.0 to 25.0 wt.-% of the builder system,
(b) 5.0 to 25.0 wt.-%, preferably 13.0 to 20.0 wt.-% of the surfactant system
(c) 35.0 to 85.0 wt.-%, preferably 55.0 to 70 wt.-% water.
3. The detergent composition according to claim 1 or 2, wherein the builder system comprises relative to the total weight of the detergent composition:
(a1 ) 1.0 to 8.0 wt.-%, preferably 3.0 to 5.0 wt.-% of the at least one inorganic builder, preferably a carbonate, more preferably sodium carbonate;
(a2) 3.0 to 15.0 wt.-%, preferably 6.0 to 10.0 wt.-% of the at least one polycarboxylic acid or salt thereof, preferably a hydroxyl group-containing polycarboxylic acid or salt thereof, more preferably citric acid or citrate, most preferably preferably sodium citrate;
(a3) 2.0 to 10.0 wt.-%, preferably 3.0 to 5.0 wt.-% of the at least one aminocarboxylate, preferably selected from the group consisting of L-glutamic acid Ī,Ī-diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine Ī,Ī'-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine Ī,Ī-diacetic acid,
hydroxyethylenediamine triacetic acid (HEDTA), and alkali metal salts thereof, more preferably GLDA tetrasodium salt;
(a4) 0.5 to 5.0 wt.%, preferably 2.0 to 3.0 wt.-% of the at least one phosphonate, preferably lysine tetra methylene phosphonate (LTMP); and
(a5) 0.5 to 5.0 wt.%, preferably 1.0 to 2.0 wt.% of the at least one acrylate-containing water-soluble polymer or acid derivative or salts thereof, preferably a sodium salt of an acrylic acid copolymer.
4. The detergent composition according to any one of claims 1 to 3, wherein the surfactant system comprises at least one, preferably two anionic surfactants, preferably being selected from the group consisting of alkyl ether sulfates and linear alkyl benzene sulfonates.
5. The detergent composition according to claim 4, wherein
(1 ) the at least one alkyl ether sulfate comprises C10-16 alkyl ether sulfates with 2 to 7 EO, preferably sodium lauryl ether sulfate with 2 EO; and/or
(2) the at least one linear alkyl benzene sulfonate (LAS) comprises linear C9-13 alkyl benzene sulfonates, preferably tridecyl benzene sulfonate sodium salt or dodecyl benzene sulfonate sodium salt; and/or
(3) the surfactant system further comprises a nonionic surfactant.
6. The detergent composition according to any one of claims 1 to 5, wherein the surfactant system comprises relative to the total weight of the detergent composition:
(1 ) 2.0 to 8.0 wt.%, preferably 3.0 to 7.0 wt.% C10-16 alkyl ether sulfates with 1 to 7 EO, preferably C12-14 fatty alcohol ether sulfates with 1-3 EO, more preferably lauryl ether sulfate with 2 EO;
(2) 3.0 to 22.0, preferably 10.0 to 15.0 wt.%, more preferably 10.0 to 15.0 wt.% of a linear alkyl benzene sulfonate, preferably dodecyl or tridecyl benzene sulfonate; and
(3) 0.0 to 10 wt.%, preferably 2.0 to 3.0 wt.%, C12-18 alkyl ethers with 1-6 EO, preferably C12-14 alkyl ethers having 1-5 EO, most preferably lauryl ether with 5 EO.
7. The detergent composition according to any one of claims 1 to 6, wherein the detergent composition further comprises at least one polymeric thickener and/or at least one polymeric stabilizer.
8. The detergent composition according to any one of claims 1 to 7, wherein the detergent composition comprises at least one, preferably two or more other substances selected from the group consisting of soaps, pH adjusting agents, perfumes, fluorescing agents (optical brighteners), dyes, colorants, antimicrobial active substances, germicides, fungicides, antioxidants, preservatives, and softening compounds.
9. Method for cleaning textiles, wherein a washing liquor containing the detergent composition according to any one of claims 1 to 8 contacts the textile in at least one method step.
10. Use of a composition comprising
(A) at least one inorganic builder, preferably a carbonate, more preferably sodium
carbonate;
(B) at least one polycarboxylic acid or salt thereof, preferably a hydroxyl group-containing polycarboxylic acid or salt thereof, more preferably citric acid or citrate;
(C) at least one aminocarboxylate, preferably selected from the group consisting of L- glutamic acid Ī,Ī-diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), imino disuccinic acid (IDS), ethylenediamine Ī,Ī'-disuccinic acid (EDDS), diethylenetriamine pentaacetic acid (DTPA), beta-alanine Ī,Ī-diacetic acid, hydroxyethylenediamine triacetic acid (HEDTA), and alkali metal salts thereof, more preferably GLDA tetrasodium salt;
(D) at least one phosphonate, preferably lysine tetra methylene phosphonate (LTMP); and
(E) at least one acrylate-containing water-soluble polymer or acid derivative or salts
thereof, preferably a sodium salt of an acrylic acid copolymer.
as a builder system in an aqueous, phosphate-free, structured liquid detergent composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102015225977 | 2015-12-18 | ||
| PCT/EP2016/081047 WO2017102868A1 (en) | 2015-12-18 | 2016-12-14 | Penta-built liquid detergent composition |
Publications (2)
| Publication Number | Publication Date |
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| EP3390607A1 true EP3390607A1 (en) | 2018-10-24 |
| EP3390607B1 EP3390607B1 (en) | 2020-02-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP16829240.7A Active EP3390607B1 (en) | 2015-12-18 | 2016-12-14 | Penta-built liquid detergent composition |
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| Country | Link |
|---|---|
| EP (1) | EP3390607B1 (en) |
| AU (1) | AU2016372352B2 (en) |
| WO (1) | WO2017102868A1 (en) |
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| US11248192B2 (en) | 2019-01-22 | 2022-02-15 | Ecolab Usa Inc. | Polymer blend to stabilize highly alkaline laundry detergent |
| EP3754005A1 (en) * | 2019-06-21 | 2020-12-23 | MolƩcula Principal - Lda | Composition and method for removing or preventing the appearance of fabric stains |
| BR112022000446A2 (en) * | 2019-07-12 | 2022-03-03 | Ecolab Usa Inc | Sprayable cleaning composition, system for applying sprayable cleaning composition with reduced mist production, and method of cleaning a hard surface using a sprayable cleaning composition with reduced mist production |
| AU2020201043A1 (en) * | 2019-10-18 | 2021-05-06 | Church & Dwight Co., Inc. | Laundry detergent composition |
| EP4256020A1 (en) * | 2020-12-07 | 2023-10-11 | Unilever IP Holdings B.V. | Detergent compositions |
| CN116583584A (en) * | 2020-12-07 | 2023-08-11 | čåå©åē„čÆäŗ§ęę§č”ęéå ¬åø | Detergent composition |
| US20240010951A1 (en) * | 2020-12-07 | 2024-01-11 | Conopco Inc., D/B/A Unilever | Detergent compositions |
| GB202109205D0 (en) * | 2021-06-25 | 2021-08-11 | Innospec Ltd | Compositions |
| DE102022113403A1 (en) | 2022-05-27 | 2023-11-30 | Henkel Ag & Co. Kgaa | Flowable detergents and cleaning agents with improved properties II |
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| EP0896998A1 (en) * | 1997-08-14 | 1999-02-17 | The Procter & Gamble Company | Laundry detergent compositions comprising a saccharide gum degrading enzyme |
| US6376450B1 (en) * | 1998-10-23 | 2002-04-23 | Chanchal Kumar Ghosh | Cleaning compositions containing multiply-substituted protease variants |
| DE102008063801A1 (en) * | 2008-12-19 | 2010-06-24 | Henkel Ag & Co. Kgaa | Machine dishwashing detergent |
| DE102009027160A1 (en) * | 2009-06-24 | 2010-12-30 | Henkel Ag & Co. Kgaa | Machine dishwashing detergent |
-
2016
- 2016-12-14 AU AU2016372352A patent/AU2016372352B2/en not_active Ceased
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| EP3390607B1 (en) | 2020-02-26 |
| AU2016372352B2 (en) | 2020-05-21 |
| AU2016372352A1 (en) | 2018-05-24 |
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