WO1998044084A9 - Particule detergente - Google Patents
Particule detergenteInfo
- Publication number
- WO1998044084A9 WO1998044084A9 PCT/US1998/006569 US9806569W WO9844084A9 WO 1998044084 A9 WO1998044084 A9 WO 1998044084A9 US 9806569 W US9806569 W US 9806569W WO 9844084 A9 WO9844084 A9 WO 9844084A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- surfactant
- particle
- hydrotrope
- weight
- viscosity
- Prior art date
Links
- 239000002245 particle Substances 0.000 title claims abstract description 148
- 239000003599 detergent Substances 0.000 title claims abstract description 130
- 239000000203 mixture Substances 0.000 claims abstract description 177
- 239000004094 surface-active agent Substances 0.000 claims abstract description 128
- 239000003752 hydrotrope Substances 0.000 claims abstract description 53
- 125000000129 anionic group Chemical group 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 238000007792 addition Methods 0.000 claims abstract description 6
- 230000002829 reduced Effects 0.000 claims abstract description 6
- -1 alkyl sulphate Chemical compound 0.000 claims description 83
- 239000011780 sodium chloride Substances 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 13
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 11
- 239000003093 cationic surfactant Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000003760 tallow Substances 0.000 claims description 6
- YNBRSWNUNPAQOF-UHFFFAOYSA-M sodium;phenylmethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC1=CC=CC=C1 YNBRSWNUNPAQOF-UHFFFAOYSA-M 0.000 claims description 4
- 238000001694 spray drying Methods 0.000 claims description 4
- 239000002752 cationic softener Substances 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 claims description 2
- JBVOQKNLGSOPNZ-UHFFFAOYSA-M 2-propan-2-ylbenzenesulfonate Chemical compound CC(C)C1=CC=CC=C1S([O-])(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-M 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims 1
- BTOWBMRQUJCRTH-UHFFFAOYSA-M sodium;4-dodecan-6-ylbenzenesulfonate Chemical compound [Na+].CCCCCCC(CCCCC)C1=CC=C(S([O-])(=O)=O)C=C1 BTOWBMRQUJCRTH-UHFFFAOYSA-M 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 64
- 239000002253 acid Substances 0.000 description 42
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 38
- 125000000217 alkyl group Chemical group 0.000 description 33
- 239000007844 bleaching agent Substances 0.000 description 28
- 125000004432 carbon atoms Chemical group C* 0.000 description 26
- 239000011734 sodium Substances 0.000 description 23
- 229940091252 Sodium supplements Drugs 0.000 description 20
- 229910052708 sodium Inorganic materials 0.000 description 20
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 19
- 102000014961 Protein Precursors Human genes 0.000 description 18
- 108010078762 Protein Precursors Proteins 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 18
- 239000002518 antifoaming agent Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 102000004190 Enzymes Human genes 0.000 description 15
- 108090000790 Enzymes Proteins 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229920000768 polyamine Polymers 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000003352 sequestering agent Substances 0.000 description 13
- 150000001204 N-oxides Chemical class 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 12
- 150000004665 fatty acids Chemical class 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 150000004967 organic peroxy acids Chemical class 0.000 description 12
- 239000000499 gel Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 150000004965 peroxy acids Chemical class 0.000 description 11
- 229920005646 polycarboxylate Polymers 0.000 description 11
- 229940088598 Enzyme Drugs 0.000 description 10
- KWIUHFFTVRNATP-UHFFFAOYSA-N Trimethylglycine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 10
- 150000008051 alkyl sulfates Chemical group 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 239000003945 anionic surfactant Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 159000000000 sodium salts Chemical group 0.000 description 9
- 230000001629 suppression Effects 0.000 description 9
- 125000002877 alkyl aryl group Chemical group 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000344 soap Substances 0.000 description 8
- 239000004367 Lipase Substances 0.000 description 7
- 229940040461 Lipase Drugs 0.000 description 7
- XCRBXWCUXJNEFX-UHFFFAOYSA-N Peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- 229910052570 clay Inorganic materials 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 235000019421 lipase Nutrition 0.000 description 7
- 108090001060 lipase Proteins 0.000 description 7
- 102000004882 lipase Human genes 0.000 description 7
- 235000021317 phosphate Nutrition 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 241000219430 Betula pendula Species 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Chemical class O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N Citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 241000048284 Potato virus P Species 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000027455 binding Effects 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 108010065511 Amylases Proteins 0.000 description 5
- 102000013142 Amylases Human genes 0.000 description 5
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- FRPJTGXMTIIFIT-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000005466 alkylenyl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-L 2-sulfobutanedioate Chemical class OS(=O)(=O)C(C([O-])=O)CC([O-])=O ULUAUXLGCMPNKK-UHFFFAOYSA-L 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinylpyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 235000019418 amylase Nutrition 0.000 description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- 150000007942 carboxylates Chemical class 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 230000003197 catalytic Effects 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000003287 optical Effects 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 229910052904 quartz Inorganic materials 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
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- 229910052682 stishovite Inorganic materials 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 229940025131 Amylases Drugs 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N DETA Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
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- 210000003141 Lower Extremity Anatomy 0.000 description 3
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- MWNQXXOSWHCCOZ-UHFFFAOYSA-M Sodium percarbonate Chemical compound [Na+].OOC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-M 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000005418 aryl aryl group Chemical group 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001860 citric acid derivatives Chemical class 0.000 description 3
- 235000019864 coconut oil Nutrition 0.000 description 3
- 239000003240 coconut oil Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical class OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 230000002366 lipolytic Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N silicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical class OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 2
- NZCIWANIJJJEML-UHFFFAOYSA-N 2-methyl-1,4,7-triazonane Chemical compound CC1CNCCNCCN1 NZCIWANIJJJEML-UHFFFAOYSA-N 0.000 description 2
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(E)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 2
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N Sodium silicate Chemical class [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 150000001450 anions Chemical group 0.000 description 2
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- 229960003237 betaine Drugs 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- OTMSDBZUPAUEDD-UHFFFAOYSA-N ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
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- 229940083124 ganglion-blocking antiadrenergic Secondary and tertiary amines Drugs 0.000 description 2
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- NERQXUOKJAXUHN-UHFFFAOYSA-L cobalt(3+);2-[3-[3-[(2-oxidophenyl)methylideneamino]propylazanidyl]propyliminomethyl]phenolate Chemical compound [Co+3].[O-]C1=CC=CC=C1C=NCCC[N-]CCCN=CC1=CC=CC=C1[O-] NERQXUOKJAXUHN-UHFFFAOYSA-L 0.000 description 1
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- VVYVUOFMPAXVCH-UHFFFAOYSA-L disodium;5-[[4-anilino-6-[2-hydroxyethyl(methyl)amino]-1,3,5-triazin-2-yl]amino]-2-[2-[4-[[4-anilino-6-[2-hydroxyethyl(methyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical group [Na+].[Na+].N=1C(NC=2C=C(C(C=CC=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(C)CCO)=CC=3)S([O-])(=O)=O)=CC=2)S([O-])(=O)=O)=NC(N(CCO)C)=NC=1NC1=CC=CC=C1 VVYVUOFMPAXVCH-UHFFFAOYSA-L 0.000 description 1
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- 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 1
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- 201000002674 obstructive nephropathy Diseases 0.000 description 1
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- 239000000123 paper Substances 0.000 description 1
- 229940055076 parasympathomimetics Choline esters Drugs 0.000 description 1
- DMCJFWXGXUEHFD-UHFFFAOYSA-N pentatriacontan-18-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)CCCCCCCCCCCCCCCCC DMCJFWXGXUEHFD-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- RRCSSMRVSNZOFR-UHFFFAOYSA-N phenyl 3,5,5-trimethylhexanoate;sodium Chemical compound [Na].CC(C)(C)CC(C)CC(=O)OC1=CC=CC=C1 RRCSSMRVSNZOFR-UHFFFAOYSA-N 0.000 description 1
- 101700004450 phpP Proteins 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
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- 239000005017 polysaccharide Substances 0.000 description 1
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- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- NJKRDXUWFBJCDI-UHFFFAOYSA-J propane-1,1,2,3-tetracarboxylate Chemical class [O-]C(=O)CC(C([O-])=O)C(C([O-])=O)C([O-])=O NJKRDXUWFBJCDI-UHFFFAOYSA-J 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical group 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-M sarcosinate Chemical compound CNCC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-M 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 150000003385 sodium Chemical group 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 229960003010 sodium sulfate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- DAPMZWDGZVFZMK-UHFFFAOYSA-N sodium;2-[2-[4-[4-[2-(2-sulfophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonic acid Chemical group [Na].[Na].OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=C(C=2C=CC(C=CC=3C(=CC=CC=3)S(O)(=O)=O)=CC=2)C=C1 DAPMZWDGZVFZMK-UHFFFAOYSA-N 0.000 description 1
- RPQSWSMNPBZEHT-UHFFFAOYSA-M sodium;2-acetyloxybenzenesulfonate Chemical compound [Na+].CC(=O)OC1=CC=CC=C1S([O-])(=O)=O RPQSWSMNPBZEHT-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- MDGXUEVTGARGDK-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane;hydrate Chemical compound O.[Na+].[O-]OB=O MDGXUEVTGARGDK-UHFFFAOYSA-M 0.000 description 1
- 230000003381 solubilizing Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003019 stabilising Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000004026 tertiary sulfonium compounds Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- GDJZZWYLFXAGFH-UHFFFAOYSA-M xylenesulfonate group Chemical group C1(C(C=CC=C1)C)(C)S(=O)(=O)[O-] GDJZZWYLFXAGFH-UHFFFAOYSA-M 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Definitions
- the present invention relates to a detergent particle for use in detergent compositions, comprising an anionic sulphonate surfactant and a hydrotrope, wherein of from 0.0% to 30% by weight of the particle of a phosphate component is present.
- the invention also relates to the use in a detergent composition or particle of a hydrotrope to reduce the viscosity of a viscous mixture, comprising a surfactant component and water, which the surfactant component forms upon contact with water
- anionic surfactants which can be partially or mostly water-soluble
- the problem is increased when the anionic surfactant is an anionic sulphonate surfactant.
- the problem can even be further increased when the (anionic sulphonate) surfactant is present in a dried particle. It is believed that gel formation can be set off by the anionic sulphonate surfactant which may tend to become 'gelly' upon contact with water, rather than dissolving completely in the water. This can then prevent delivery of other components of the detergent into the wash water.
- the Applicants have now found that the problem of gel formation and poor dispensing can be solved or ameliorated by the incorporation of a hydrotrope into the detergent composition or in particular into the detergent particle, comprising the (anionic sulphonate) surfactant.
- hydrotropes are known in the art as compounds which have the property to increase the solubility of slightly soluble compounds.
- WO 95/30730 describes hydrotropes as an aid for phase stabilisation in liquid detergents.
- US 3,926,827 describes hydrotropes as components which can retain oxygen bubbles, giving the detergent more volume.
- GB 1591516 describes hydrotropes as a process aid to obtain free-flowing detergent mixtures.
- the use of hydrotropes in granular detergent compositions comprising anionic sulphonate surfactant to obtain improved dispensing of the detergent composition is not known in the art.
- the hydrotrope reduces the viscosity of gels formed by the (sulphonate) surfactant, present in the detergent particle or detergent composition, upon contact with water. This produces improved dispensing of the detergent composition into the wash water by minimising the formation of insoluble clumps or gels or residues in the machine. Reduction of the detergent clumps, residues or gels in the machine and in particular in the dispensing drawer or dispensing device, leads to a cleaner appearance of the washing machine and more efficient performance of the detergent composition.
- a detergent particle comprising an anionic sulphonate surfactant present at a level of from 0.01% to 20% by weight of the particle and a hydrotrope present at a level of from 0.01% to 45.0% by weight of the particle, wherein from 0.0% to 30% by weight of the particle of a phosphate component may be present.
- the particle can be used in a detergent composition, in accord with the invention.
- the invention also provides improved dispensing of a detergent composition by the use of a hydrotrope in a detergent composition or particle, comprising a surfactant component, preferably comprising an anionic sulphonate surfactant (wherein the surfactant component preferably has a viscosity of at least 15000 cp in a 25% by weight solution in water at 20°C, as measured by the Surfactant Viscosity Test), wherein on addition of the hydrotrope to the surfactant component, the viscosity of the surfactant component is reduced, preferably by at least 25%.
- a surfactant component preferably comprising an anionic sulphonate surfactant
- the surfactant component preferably has a viscosity of at least 15000 cp in a 25% by weight solution in water at 20°C, as measured by the Surfactant Viscosity Test
- the hydrotrope of the present invention is used in detergent compositions or particles, comprising a surfactant component, to reduce the viscosity of the surfactant component upon contact with water.
- the hydrotrope is added to the surfactant component to reduce the viscosity thereof in water.
- the invention is preferably such that a surfactant component which has a first viscosity of at least 15000 cP in a 25% by weight solution in water at 20°C, as measured by the Surfactant Viscosity Test as described below, has when a hydrotrope is used in the surfactant component, a viscosity which is 25% less then the first viscosity.
- the surfactant component comprises one or more surfactants, selected from the surfactants as described herein.
- the hydrotrope is used in a spray-dried particle, comprising an anionic sulphonate surfactant, which form upon contact with water a viscous mixture, comprising the surfactant and water, having a viscosity of at least 15000 cP in a 25% by weight solution in water at 20°C, as measured by the Surfactant Viscosity Test.
- the viscosity of the surfactant component which comprises all of the surfactants of the detergent composition or the particle, in the respective ratio's and levels, in a solution of water is measured.
- the viscosity A of a surfactant component in water is determined:
- the surfactant component is such that the viscosity A is at least 15000 cP, more preferably at least 18000 cP.
- Viscosity A-Viscositv B x 100% reduction of viscosity (in %). Viscosity A
- the hydrotrope and the amount thereof is preferably such that the reduction of viscosity is at least 25%, preferably more then 30%, most preferably more then 40%.
- the particle of the invention can be used in a detergent composition.
- the detergent composition may consist essentially of such particles, but preferably the detergent composition comprises the particles and other components, having a different chemical composition, and optionally hydrotropes and anionic sulphonate surfactants.
- the particle of the invention is present in a detergent composition, preferably phosphate-free compositions, at a level of from 5% to 85%, more preferably from 10% to 70%, most preferably from 30% to 60% by weight of the composition.
- a detergent composition preferably phosphate-free compositions
- the particle of the invention comprises an anionic sulphate surfactant, preferably present at a level of from 0.01% to 50%, more preferably from 1% to 20%, most preferably from 2% to 10% by weight of the particle.
- the particle of the invention are formed by a process, which includes a drying step.
- the drying step produces a dried particle, generally having a free-moisture content below 6% by weight, preferably less than 1%, or more preferably less than 0.5%, or most preferably less than 0.25% by weight.
- free-moisture content is determined by placing 5 grams of a sample of base detergent granules in a petri dish, placing the sample in a convection oven at 50°C (122°F) for 2 hours, followed by measurement of the weight loss due to water evaporation.
- the particle of the invention are formed in a process whereby a paste or slurry or crutcher mix comprising the anionic sulphonate surfactant, is formed into particles and dried, as known in the art.
- a preferred process spray-drying.
- a preferred process for manufacturing the particles comprises preparing an aqueous solution-dispersion, commonly referred to as a past or slurry or crutcher mix, is prepared, comprising the components of the final particle.
- aqueous solution-dispersion commonly referred to as a past or slurry or crutcher mix
- the crutcher mix will usually be of as high a solids content as feasible, e.g., 40% to 80%, with the balance, e.g. 20% to 60%, being water. More water may be used but then energy demands are increased, tower throughput are diminished, products resulting may be tackier and poorer flowing g and often the desired low density base and final detergent composition particles will not be obtained.
- the most preferred method is spray drying, wherein the crutcher mix is sprayed at an elevated pressure (usually from 3 to 50 kg/cm ⁇ , preferably 20 to 40kg/cm2) through one or more spray nozzles into a drying tower, through which drying air passes to dry the resulting droplets of crutcher mix to globular the particles.
- spray nozzles equivalent atomisers of other designs may also be used.
- the preferred spray tower design is counter-current, the height of the tower usually being from 5 to 25 meters and the entering hot air, usually the gaseous products of combustion of oil or gas, being at a temperature in the range of from 200° to 400°C and the outlet air usually at a temperature in the range of from 50° to 90°C.
- Concurrent tower designs may also be employed wherein similar inlet and outlet air temperatures obtain.
- the nozzle size for producing droplets of crutcher mix will be chosen such particles of the preferred particle size are formed, preferably of from 0.1 mm to 3.0 mm. Preferably, substantially all the particles are within this range when removed from the spray tower, but any off-size particles can be removed by screening, may be size- reduced to the desired size range or may be recycled in the same or a subsequent crutcher mix.
- the anionic sulphate surfactant When an anionic sulphate surfactant is present in the final particle, the anionic sulphate surfactant will be comprised in the crutcher mix, together with the hydrotrope and the anionic sulphonate surfactant.
- the crutcher mix is substantially free from nonionic surfactant and/ or cationic softeners or cationic surfactant.
- the particle of the invention is preferably substantially free from nonionic surfactant and/ or cationic softeners or cationic surfactant.
- the particle comprises of from 0.0% to 30%, more preferably from 0.0% to 20%, most preferably from 0.0% to 8% by weight of the particle of a phosphate component. It can be particular useful for the present invention that the anionic sulphonate surfactant and the hydrotrope are present in a substantially phosphate-free particle.
- additional detergent components can be added to the particles, preferably by spraying the molten component, which may be in concentrated aqueous solution but preferably is free of water, onto the surfaces of the tumbling base particles in an inclined drum, through which the particles progress from an elevation feed end to the discharge end.
- the molten component which may be in concentrated aqueous solution but preferably is free of water
- the particle can be introduced to a detergent composition by any method, known in the art.
- the particles are dry-added to the other detergent ingredients.
- the level of anionic sulphonate surfactant in the particle is from 0.01% to 20%, preferably from 0.5% to 18%, more preferably from 3% to 15%, most preferably from 5% to 15% by weight of the particle.
- the ratio of anionic sulphonate surfactant to the hydrotrope in the particle is preferably from 50:1 to 1:1, more preferably from 25:1 to 1:1, most preferably from 10:1 to 2:1.
- Anionic sulfonate surfactants suitable for use herein include the salts (or optionally the acids) of C5-C20 linear or branched alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, preferably derived from alcohols derived from tallow or coconut oil, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
- the cation of the anionic sulphonate surfactant may be hydrogen, ammonium or alcohol amine, but preferably sodium or potassium.
- a highly preferred anionic sulphonate surfactant is a sodium or potassium salt of CjQ-Cig, preferably CJQ-CIO, most preferably C ⁇ 1-C13, branched or more preferably, linear alkylbenzene sulfonates.
- a hydrotrope is present in the particle or used in a particle or detergent composition.
- the surfactant component or particularly the anionic sulphonate surfactant (comprised in the surfactant component), comprised in the particle or detergent composition, forms upon contact with water a viscous mixture, as described above.
- the hydrotrope is used to reduce the viscosity of the mixture.
- hydrotrope when used herein is meant any of the hydrotropes known in the art, capable of reducing the viscosity of a mixture, comprising water and a surfactant component, in particular comprising a an anionic sulphonate surfactant.
- hydrotropes there can be mentioned the short-chain (C1-C4) alk-aryl sulfonates.
- the invention herein should be understood to cover sulfonic acid.
- the hydrotrope component exists primarily as the ionized salt, when water, even small amount, are present during the formulation of the particle or the composition comprising the particle.
- the hydrotrope may be added to the composition in its acidic form, it is likely to appear in the formula as a salt derivative.
- the water-soluble salts useful in the present invention include the alkali metal, alkaline earth metal, alkyl amine and ammonium salts of the sulfonic acid.
- Preferred salts are sodium, potassium, and monoethanolamine sulfonate, and mixtures thereof.
- the toluene sulfonates, the cumene sulfonates, the xylene sulfonates may be used in this invention.
- a sodium toluene sulfonate being preferably a sodium toluene mono sulfonate .
- the level of the hydrotrope in the particle is from 0.01% to 45%, preferably from 0.1% to 15%, more preferably from 0.2% to 5%, even more preferably from 0.5% to 2%, most preferably from 0.8% to 1.8% by weight of the particle
- the detergent composition can comprise additional hydrotrope.
- a highly preferred additional anionic surfactant to be present in the detergent composition and most preferably (partially) in the dried particle of the present invention can be an anionic sulphate surfactant.
- anionic sulfate surfactants when used herein, is meant the linear and branched primary and secondary alkyl sulfates, alkyl ether sulphates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N-(Cj-C4 alkyl) and -N-(Cj-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
- Alkyl sulfate surfactants are most preferably selected from the linear and branched primary C ⁇ ⁇ -C ⁇ g alkyl sulfates, more preferably the C ⁇ ⁇ -C ⁇ 5 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
- a highly preferred sulphate surfactant are the sodium or potassium salts of the sulphates, produced by sulphating Cg-Cjg alcohols derived from tallow or coconut oil. Also highly preferred can be the sodium or potassium salts of the sulphates C16-C18 alcohols derived from palmeric fatty acid or stearic fatty acid.
- the cation of the anionic sulphate surfactant may be hydrogen, ammonium or alcohol amine, but preferably sodium or potassium.
- the anionic sulphate surfactant is preferably present at a level of from 0.01% to 50%, more preferably from 1% to 20%, most preferably from 2% to 10% by weight of the particle.
- the particle and/ or the detergent compositions, comprising the particle of the invention may also contain additional ingredients or components.
- additional ingredients, and levels of incorporation thereof will depend on the physical form of the final composition, and the precise nature of the washing operation for which it is to be used.
- the particle preferably comprises as an additional ingredient one or more builders, preferably alumino silicates and/ or organic polycarboxylate polymers, alkali sources, or mixtures thereof.
- the particle is substantially free from nonionic and/ or cationic surfactants.
- the detergent compositions comprising the particle of the invention, preferably contain one or more additional detergent components selected from additional surfactants, bleach, bleach activators, acid sources, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
- additional surfactants selected from additional surfactants, bleach, bleach activators, acid sources, builders, organic polymeric compounds, enzymes, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.
- additional anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants is given in U.S.P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
- a list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March
- the detergent composition and/ or the particle in accord with the present invention can comprise one or more additional anionic surfactants.
- any anionic surfactants useful for detersive purposes can be comprised in the detergent composition or optionally in the particle. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono- di- and triethanolamine salts) of the alkyl ethoxy sulphate, carboxylate and sarcosinate surfactant.
- anionic surfactants include the isethionates such as the acyl isethionates, N- acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C- j ⁇ -C-
- Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
- the level of anionic surfactant in the detergent composition is preferably from 4% to 60%, more preferably from 6% to 30%, most preferably from 10% to 20% by weight.
- Alkyl ethoxysulfate surfactants are preferably from 4% to 60%, more preferably from 6% to 30%, most preferably from 10% to 20% by weight.
- Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the CjQ-Cig alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Ci i-Cjg, most preferably C ⁇ ⁇ -C ⁇ 5 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
- Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
- Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2C00"M + wherein R is a C to C ⁇ g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
- Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR ⁇ -CHR2-O)-R3 wherein R is a Cg to Cjg alkyl group, x is from 1 to 25, R ⁇ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
- Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
- Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2- propyl-1-nonanoic acid, 2-butyl-l-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.
- alkali metal sarcosinates of formula R- CON (R 1 ) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R! is a C1-C4 alkyl group and M is an alkali metal ion.
- R is a C5-C17 linear or branched alkyl or alkenyl group
- R! is a C1-C4 alkyl group
- M is an alkali metal ion.
- Suitable surfactant useful in the detergent composition, comprising the particle is one or more cationic surfactants.
- Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono Cg-C ⁇ g, preferably Cg-CjQ N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
- Another preferred cationic surfactant is an Cg-Cjg alkyl or alkenyl ester of an quaternary ammonium alcohol, such as quaternary choline esters.
- the level of cationic surfactant is preferably from 0.2% to 20%, more preferably from 0.5% to 15%, even more preferably from 1% to 10%, most preferably from 1% to 5% by weight of the composition.
- the detergent composition comprising the particle of the present invention can contain a nonionic surfactant.
- the particle preferably does not comprise nonionic surfactant.
- the nonionics can be sprayed on the particle of the invention. Essentially any nonionic surfactant can be used herein.
- the level of nonionic surfactant is preferably from 1% to 30%, more preferably from 2% to 25%, even more preferably from 3% to 15%, most preferably from 4% to 12% by weight of the composition.
- any alkoxylated nonionic surfactants are suitable herein.
- the ethoxylated and propoxylated nonionic surfactants are preferred.
- Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
- the condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
- the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
- Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
- Nonionic polyhydroxy fatty acid amide surfactant Nonionic polyhydroxy fatty acid amide surfactant
- Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R 2 CONR!Z wherein : Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C alkyl (i.e., methyl); and R2 is a C5- C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9-C ⁇ 7 alkyl or alkenyl, most preferably straight-chain C ⁇ ⁇ -C j 7 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated
- Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
- Suitable fatty acid amide surfactants include those having the formula: R6CON(R )2 wherein R > is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon atoms and each R ⁇ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from l to 3.
- R6CON(R )2 R > is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon atoms and each R ⁇ is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) x H, where x is in the range of from l to 3.
- Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
- Preferred alkylpolyglycosides have the formula
- R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8.
- the glycosyl is preferably derived from glucose.
- Optional amphoteric surfactants for use in the particle or detergent compositions, comprising the particle include the amine oxide surfactants and the alkyl amphocarboxylic acids.
- Suitable amine oxides include those compounds having the formula R3(OR4) X NO(R5)2 wherein R ⁇ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
- Preferred are C j Q -Cig alkyl dimethylamine oxide, and Cjo-lg acylamido alkyl dimethylamine oxide.
- a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ. Zwitterionic surfactant
- zwitterionic surfactants can be incorporated into the detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
- Suitable betaines are those compounds having the formula R(R')2N + R 2 COO ⁇ wherein R is a C6-Cjg hydrocarbyl group, each R! is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
- Preferred betaines are Cj2-lg dimethyl-ammonio hexanoate and the Cjo-lg acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
- Complex betaine surfactants are also suitable for use herein.
- the particle and/ or the detergent compositions of the present invention can contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
- Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.
- the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
- Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
- Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
- Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
- Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
- Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
- Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
- Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
- Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
- the particle and/ or the detergent compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present in the detergent composition at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
- the partially soluble or insoluble builder compound is preferably present at a level of from 5% to 85% by weight, preferably from 15% to 60% by weight, most preferably from 20% to 50% weight of the particle.
- largely water insoluble builders include the sodium aluminosilicates.
- Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO2) z (SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
- the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
- the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula
- Zeolite X has the formula Na 6 [(AlO 2 )g6(SiO2)i06]- 2 76 H 2 O.
- the particle of the invention does not comprise a crystalline layered silicate.
- preferred crystalline layered silicates for use in the detegrent compositions herein have the general formula
- M is sodium or hydrogen
- x is a number from 1.9 to 4 and y is a number from 0 to 20.
- Crystalline layered sodium silicates of this type are disclosed in EP-A- 0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE- A-3742043.
- x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2.
- the most preferred material is ⁇ -Na2Si2 ⁇ 5, available from Hoechst AG as NaSKS-6. Perhvdrate bleaches
- An preferred additional components of the detergent composition and/ or detergent particle is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts.
- Perborate can be mono or tetra hydrated.
- Sodium percarbonate has the formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
- Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
- a preferred feature of detergent particle and/or composition is an organic peroxyacid bleaching system.
- the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
- the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
- Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleach of the claimed invention.
- a preformed organic peroxyacid is incorporated directly into the composition.
- Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
- Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
- peroxyacid bleach precursors may be represented as
- L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is O
- Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
- Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
- Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
- Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.
- L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
- Preferred L groups are selected from the group consisting of:
- R is an alkyl, aryl, or alkaryl group containing from
- R 3 is an alkyl chain containing from 1 to 8 carbon atoms
- R 4 is H or R 3
- Y is H or a solubilizing group. Any of R 1 , R3 and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups.
- M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
- M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
- Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
- Preferred precursors of this type provide peracetic acid on perhydrolysis.
- Preferred alkyl percarboxylic precursor compounds of the imide type include the N- tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
- Tetraacetyl ethylene diamine (TAED) is particularly preferred.
- the TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.
- alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
- Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:
- R! is an alkyl group with from 1 to 14 carbon atoms
- R 2 is an alkylene group containing from 1 to 14 carbon atoms
- R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
- Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
- Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
- Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
- Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole.
- Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
- Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
- cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
- Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.
- the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
- the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.
- Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
- Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
- Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.
- precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
- R * is H, alkyl, alkaryl, aryl, or arylalkyl.
- the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.
- a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
- R S an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
- R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
- R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
- organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
- diacyl and tetraacylperoxides especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid.
- Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
- the particle or the compositions optionally contain a transition metal containing bleach catalyst.
- a transition metal containing bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
- Such catalysts are disclosed in U.S. Pat. 4,430,243.
- bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include O) 1 (u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Cl ⁇ 4)2, Mn IV 4(u- O)6(l,4,7-triazacyclononane)4-(Cl ⁇ 4)2, Mn I Mn IV 4(u-O) ⁇ (u-OAc)2-(l,4,7- trimethyl-l,4,7-triazacyclononane)2-(Cl ⁇ 4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272.
- ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, 1 ,2,4,7 -tetramethyl- 1,4,7-triazacyclononane, and mixtures thereof.
- bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane)(OCH3)3_(PF6).
- Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water- soluble complex of manganese (III), and/or (IV) with a ligand which is a non- carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
- binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands including N4MnIH(u-O)2MnIVN4) + and [Bipy2MnIH(u- O) 2 MnIVbip y2 ]-(Cl ⁇ 4)3.
- bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
- An acid source, or source of acidity can be present in the particle or in the detergent composition.
- an alkali source present, capable of reacting with the acid source to produce a gas.
- the level of the acid source in the particle or detegrent composition is preferably from 0.5% to 10 %, more preferably from 1% to 7%, most preferably from 2% to 5% by weight of the particle or composition.
- the source of acidity is preferably non-hygroscopic, which can improve storage stability.
- monohydrates acids can also be useful herein.
- Organic acids and their derivatives are preferred.
- the acid is preferably water-soluble. Suitable acids include citric, glutaric, succinic or adipic acid, monosodium phosphate, sodium hydrogen sulfate, boric acid, or a salt or an ester thereof. Citric acid is especially preferred.
- the particle and/or the detergent compositions, comprising the particle of the invention preferably contain as an optional component a heavy metal ion sequestrant.
- heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
- Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1% to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.
- Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates.
- Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.
- Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
- Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133.
- iminodiacetic acid-N-2- hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl- 3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
- EP-A-476,257 describes suitable amino based sequestrants.
- EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
- EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2- phosphonobutane-l,2,4-tricarboxylic acid are also suitable.
- Glycinamide-N,N'- disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2- hydroxypropylenediamine-N-N' -disuccinic acid (HPDDS) are also suitable.
- Enzyme Another preferred ingredient useful in the detergent compositions, comprising the particle, or optionally of the particle is one or more additional enzymes.
- the enzymes or part thereof cam be present in the agglomerated or extruded particle of the invention.
- Preferred additional enzymatic materials include the commercially available Upases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
- protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
- Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.
- Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo).
- Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
- Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.
- Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
- the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain ofHumicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
- a preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
- Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge- Jensen et al, issued March 7, 1989.
- Organic polymeric compounds are preferred additional components of the particle and/ or the detergent compositions, comprising the particle in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
- organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.
- Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most preferably from 1% to 10% by weight of the compositions.
- organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
- Polymers of the latter type are disclosed in GB-A- 1,596,756.
- salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.
- polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
- Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.
- Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
- organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
- Another organic compound which is a preferred clay dispersant/ anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:
- X is a nonionic group selected from the group consisting of H, C1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof
- a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene)
- the detergent compositions when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
- Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
- antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
- Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
- silicone antifoam compounds as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
- Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
- Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
- the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
- Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
- Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ⁇ g-C4Q ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to terra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
- high molecular weight fatty esters e.g. fatty acid triglycerides
- fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
- a preferred suds suppressing system comprises preferably a silicone antifoam compound comprising in combination
- silica at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound
- silica/silicone antifoam compound is incorporated at a level of from 5% to 50%, preferably 10% to 40% by weight;
- a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight;
- a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;
- an inert carrier fluid compound most preferably comprising a C ⁇ (,-C ⁇ g ethoxylated alcohol with a degree of ethoxy lation of from 5 to 50, preferably
- a highly preferred particulate suds suppressing system is described in EP-A- 0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
- EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
- Clay softening system The particle and/ or the detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.
- the clay mineral compound is preferably a smectite clay compound.
- Smectite clays are disclosed in the US Patents Nos. 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
- European Patents Nos. EP-A-299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
- the particle but preferably the detergent compositions may also comprise from 0.01% to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
- the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
- Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :
- A is NC ll, CllO, C II, -O-, -S-, -N-; x is O or 1 ; R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
- the N-O group can be represented by the following general structures :
- Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.
- the N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.
- Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
- R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups.
- One class of said polyamine N- oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
- Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
- polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit.
- a preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
- R is an aromatic,heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group.
- R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
- the polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.
- Suitable herein are coploymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000.
- the preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.
- the detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000.
- PVP polyvinylpyrrolidone
- Suitable polyvinylpyrrolidones are commercially valuable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
- PVP K-15 is also available from ISP Corporation.
- Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.
- the detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents.
- Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.
- the detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent.
- Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.
- the detergent compositions herein also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
- Hydrophilic optical brighteners useful herein include those having the structural formula:
- R ⁇ is selected from anilino, N-2-bis-hydroxyethyl and NH-2 -hydroxyethyl
- R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino
- M is a salt-forming cation such as sodium or potassium.
- R ⁇ is anilino
- R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
- the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
- R ⁇ is anilino
- R2 is N-2-hydroxyethyl-N-2- methylamino
- M is a cation such as sodium
- the brightener is 4,4'-bis[(4-anilino- 6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
- R ⁇ is anilino
- R2 is morphilino
- M is a cation such as sodium
- the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
- This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
- Other optional ingredients are commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
- compositions suitable for inclusion in the particle and/or the detergent compositions include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
- the particle and/or the final detergent composition preferably have a pH measured as a 1% solution in distilled water of at least 10.0, preferably from 10.0 to 12.5, most preferably from 10.5 to 12.0.
- compositions comprising the particle, can take a variety of physical forms, preferably granular.
- the compositions can be of the form of a low- density granular detergent composition or the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load, or can be added to the wash by means of a dispensing drawer, or can be added freely into the machine, preferably on the bottom of the machine.
- the mean particle size of the base composition of granular compositions in accordance with the invention can be from 0.1 mm to 5.0 mm, but it should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
- mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
- the bulk density of granular detergent compositions is typically of at least 500 g/litre, more preferably from 650 g/litre to 1200 g/litre.
- Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
- the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
- the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
- the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
- the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
- the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
- Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention.
- an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
- Nai2(Al ⁇ 2Si ⁇ 2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers
- Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m
- Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400 ⁇ m and 1200 ⁇ m
- MA/AA Copolymer of 1 :4 maleic/acrylic acid average molecular weight about 70,000.
- NAC-OBS Nonanamido caproyl oxybenzene sulfonate in the form of the sodium salt.
- TAED Tetraacetylethylenediamine DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the
- Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
- Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5- triazin-2-yl)amino) stilbene-2:2'-disulfonate.
- Formulation N is particularly suitable for usage under Japanese machine wash conditions.
- Formulations O to S are particularly suitable for use under US machine wash conditions.
Abstract
L'invention concerne l'amélioration de la distribution d'une composition ou d'une particule détergente au moyen d'un hydrotrope dans une composition ou une particule détergente, comprenant un constituant tensio-actif, renfermant de préférence un tensio-actif à sulfonates anioniques, et dans laquelle lors de l'addition de l'hydrotrope au constituant tensio-actif, la viscosité du constituant tensio-actif dans l'eau est réduite. L'invention concerne également une particule détergente destinée à être utilisée dans des compositions détergentes, comprenant un tensio-actif à sulfonates anioniques dont le niveau est compris entre 0,01 % et 20 % en poids de la particule, ainsi qu'un hydrotrope dont le niveau est compris entre 0,01 % et 45,0 % en poids de la particule, le constituant phosphate représentant 0,0 % à 30 % en poids de la particule.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9808457-7A BR9808457A (pt) | 1997-04-02 | 1998-04-02 | Partìculas detergente |
EP98913387A EP0985011A4 (fr) | 1997-04-02 | 1998-04-02 | Particule detergente |
HU0001742A HUP0001742A2 (hu) | 1997-04-02 | 1998-04-02 | Mosószerkészítmények szemcsés anyag komponense |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9706671A GB2323848A (en) | 1997-04-02 | 1997-04-02 | Detergent particle |
GB9706671.6 | 1997-04-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1998044084A1 WO1998044084A1 (fr) | 1998-10-08 |
WO1998044084A9 true WO1998044084A9 (fr) | 1999-03-11 |
Family
ID=10810151
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/006569 WO1998044084A1 (fr) | 1997-04-02 | 1998-04-02 | Particule detergente |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0985011A4 (fr) |
CN (1) | CN100366715C (fr) |
AR (1) | AR015325A1 (fr) |
BR (1) | BR9808457A (fr) |
GB (1) | GB2323848A (fr) |
HU (1) | HUP0001742A2 (fr) |
WO (1) | WO1998044084A1 (fr) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE29905721U1 (de) * | 1999-03-27 | 1999-06-10 | Henkel Kgaa | Alkylbenzolsulfonat-Granulate |
EA002961B1 (ru) | 1999-03-30 | 2002-12-26 | Унилевер Нв | Моющие порошкообразные композиции |
DE10160319B4 (de) * | 2001-12-07 | 2008-05-15 | Henkel Kgaa | Tensidgranulate und Verfahren zur Herstellung von Tensidgranulaten |
EP1352951A1 (fr) * | 2002-04-11 | 2003-10-15 | The Procter & Gamble Company | Granulé détergent comprenant un tensioactif nonionique et une hydrotrope |
MX2019010930A (es) * | 2017-03-16 | 2020-01-21 | Procter & Gamble | Suspensiones de partículas de suministro que contienen agentes benéficos. |
CA3054549C (fr) | 2017-03-16 | 2022-12-13 | The Procter & Gamble Company | Particules de distribution contenant un agent benefique |
WO2023025685A1 (fr) | 2021-08-27 | 2023-03-02 | Unilever Ip Holdings B.V. | Composition détergente |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA995092A (en) * | 1972-07-03 | 1976-08-17 | Rodney M. Wise | Sulfated alkyl ethoxylate-containing detergent composition |
US3926827A (en) * | 1973-03-29 | 1975-12-16 | Colgate Palmolive Co | Method for making detergent compositions |
US4289640A (en) * | 1974-01-21 | 1981-09-15 | Colgate-Palmolive Company | Cleaning compositions |
CA2027518A1 (fr) * | 1990-10-03 | 1992-04-04 | Richard L. Tadsen | Methode de preparation de compositions detergentes a haute densite, contenant des particules tensio-actives sensibles au ph |
DE4203031A1 (de) * | 1992-02-04 | 1993-08-05 | Henkel Kgaa | Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit |
US5478502A (en) * | 1994-02-28 | 1995-12-26 | The Procter & Gamble Company | Granular detergent composition containing hydrotropes and optimum levels of anoionic surfactants for improved solubility in cold temperature laundering solutions |
US5478503A (en) * | 1994-02-28 | 1995-12-26 | The Procter & Gamble Company | Process for making a granular detergent composition containing succinate hydrotrope and having improved solubility in cold temperature laundering solutions |
US5569645A (en) * | 1995-04-24 | 1996-10-29 | The Procter & Gamble Company | Low dosage detergent composition containing optimum proportions of agglomerates and spray dried granules for improved flow properties |
US5756444A (en) * | 1996-11-01 | 1998-05-26 | The Procter & Gamble Company | Granular laundry detergent compositions which are substantially free of phosphate and aluminosilicate builders |
-
1997
- 1997-04-02 GB GB9706671A patent/GB2323848A/en not_active Withdrawn
-
1998
- 1998-04-02 AR ARP980101501A patent/AR015325A1/es unknown
- 1998-04-02 EP EP98913387A patent/EP0985011A4/fr not_active Withdrawn
- 1998-04-02 BR BR9808457-7A patent/BR9808457A/pt not_active Application Discontinuation
- 1998-04-02 WO PCT/US1998/006569 patent/WO1998044084A1/fr not_active Application Discontinuation
- 1998-04-02 CN CNB988054388A patent/CN100366715C/zh not_active Expired - Fee Related
- 1998-04-02 HU HU0001742A patent/HUP0001742A2/hu unknown
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