CA2336666A1 - Laundry and cleaning compositions - Google Patents
Laundry and cleaning compositions Download PDFInfo
- Publication number
- CA2336666A1 CA2336666A1 CA002336666A CA2336666A CA2336666A1 CA 2336666 A1 CA2336666 A1 CA 2336666A1 CA 002336666 A CA002336666 A CA 002336666A CA 2336666 A CA2336666 A CA 2336666A CA 2336666 A1 CA2336666 A1 CA 2336666A1
- Authority
- CA
- Canada
- Prior art keywords
- perfume
- acid
- methyl
- composition
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 209
- 238000004140 cleaning Methods 0.000 title claims abstract description 38
- 239000002304 perfume Substances 0.000 claims abstract description 122
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 47
- 229920001002 functional polymer Polymers 0.000 claims abstract description 32
- 239000004615 ingredient Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- -1 polyoxyethylene Polymers 0.000 claims description 67
- 239000004744 fabric Substances 0.000 claims description 60
- 150000001875 compounds Chemical class 0.000 claims description 50
- 150000001412 amines Chemical class 0.000 claims description 44
- 239000004927 clay Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 150000001299 aldehydes Chemical class 0.000 claims description 21
- 150000002576 ketones Chemical class 0.000 claims description 21
- 239000003205 fragrance Substances 0.000 claims description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 13
- 229920000656 polylysine Polymers 0.000 claims description 11
- 125000003277 amino group Chemical group 0.000 claims description 10
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010348 incorporation Methods 0.000 claims description 10
- 229930002839 ionone Natural products 0.000 claims description 10
- VAMXMNNIEUEQDV-UHFFFAOYSA-N methyl anthranilate Chemical compound COC(=O)C1=CC=CC=C1N VAMXMNNIEUEQDV-UHFFFAOYSA-N 0.000 claims description 10
- 150000003335 secondary amines Chemical group 0.000 claims description 10
- 108010039918 Polylysine Proteins 0.000 claims description 9
- 229920001308 poly(aminoacid) Polymers 0.000 claims description 9
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 claims description 8
- KVWWIYGFBYDJQC-UHFFFAOYSA-N methyl dihydrojasmonate Chemical compound CCCCCC1C(CC(=O)OC)CCC1=O KVWWIYGFBYDJQC-UHFFFAOYSA-N 0.000 claims description 8
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims description 8
- 150000002499 ionone derivatives Chemical class 0.000 claims description 7
- XEJGJTYRUWUFFD-FNORWQNLSA-N (e)-1-(2,6,6-trimethyl-1-cyclohex-3-enyl)but-2-en-1-one Chemical compound C\C=C\C(=O)C1C(C)C=CCC1(C)C XEJGJTYRUWUFFD-FNORWQNLSA-N 0.000 claims description 6
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 6
- ORMHZBNNECIKOH-UHFFFAOYSA-N 4-(4-hydroxy-4-methylpentyl)cyclohex-3-ene-1-carbaldehyde Chemical compound CC(C)(O)CCCC1=CCC(C=O)CC1 ORMHZBNNECIKOH-UHFFFAOYSA-N 0.000 claims description 5
- POIARNZEYGURDG-FNORWQNLSA-N beta-damascenone Chemical compound C\C=C\C(=O)C1=C(C)C=CCC1(C)C POIARNZEYGURDG-FNORWQNLSA-N 0.000 claims description 5
- 229940102398 methyl anthranilate Drugs 0.000 claims description 5
- PHXATPHONSXBIL-UHFFFAOYSA-N xi-gamma-Undecalactone Chemical compound CCCCCCCC1CCC(=O)O1 PHXATPHONSXBIL-UHFFFAOYSA-N 0.000 claims description 5
- 229930007850 β-damascenone Natural products 0.000 claims description 5
- OFHHDSQXFXLTKC-UHFFFAOYSA-N 10-undecenal Chemical group C=CCCCCCCCCC=O OFHHDSQXFXLTKC-UHFFFAOYSA-N 0.000 claims description 4
- NFAVNWJJYQAGNB-UHFFFAOYSA-N 2-methylundecanal Chemical compound CCCCCCCCCC(C)C=O NFAVNWJJYQAGNB-UHFFFAOYSA-N 0.000 claims description 4
- OHRBQTOZYGEWCJ-UHFFFAOYSA-N 3-(3-propan-2-ylphenyl)butanal Chemical compound CC(C)C1=CC=CC(C(C)CC=O)=C1 OHRBQTOZYGEWCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- KMPQYAYAQWNLME-UHFFFAOYSA-N Undecanal Natural products CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 claims description 4
- HMKKIXGYKWDQSV-KAMYIIQDSA-N alpha-Amylcinnamaldehyde Chemical compound CCCCC\C(C=O)=C\C1=CC=CC=C1 HMKKIXGYKWDQSV-KAMYIIQDSA-N 0.000 claims description 4
- CRIGTVCBMUKRSL-UHFFFAOYSA-N alpha-Damascone Natural products CC=CC(=O)C1C(C)=CCCC1(C)C CRIGTVCBMUKRSL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 4
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 claims description 4
- HZYHMHHBBBSGHB-UHFFFAOYSA-N (2E,6E)-2,6-Nonadienal Natural products CCC=CCCC=CC=O HZYHMHHBBBSGHB-UHFFFAOYSA-N 0.000 claims description 3
- HZYHMHHBBBSGHB-DYWGDJMRSA-N (2e,6e)-nona-2,6-dienal Chemical compound CC\C=C\CC\C=C\C=O HZYHMHHBBBSGHB-DYWGDJMRSA-N 0.000 claims description 3
- 239000001674 (E)-1-(2,6,6-trimethyl-1-cyclohexenyl)but-2-en-1-one Substances 0.000 claims description 3
- FVUGZKDGWGKCFE-UHFFFAOYSA-N 1-(2,3,8,8-tetramethyl-1,3,4,5,6,7-hexahydronaphthalen-2-yl)ethanone Chemical compound CC1(C)CCCC2=C1CC(C(C)=O)(C)C(C)C2 FVUGZKDGWGKCFE-UHFFFAOYSA-N 0.000 claims description 3
- BGTBFNDXYDYBEY-UHFFFAOYSA-N 1-(2,6,6-trimethylcyclohexen-1-yl)but-2-en-1-one Chemical compound CC=CC(=O)C1=C(C)CCCC1(C)C BGTBFNDXYDYBEY-UHFFFAOYSA-N 0.000 claims description 3
- CTLDWNVYXLHMAS-UHFFFAOYSA-N 2,4,4,7-tetramethyloct-6-en-3-one Chemical compound CC(C)C(=O)C(C)(C)CC=C(C)C CTLDWNVYXLHMAS-UHFFFAOYSA-N 0.000 claims description 3
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 claims description 3
- BGTBFNDXYDYBEY-FNORWQNLSA-N 4-(2,6,6-Trimethylcyclohex-1-enyl)but-2-en-4-one Chemical compound C\C=C\C(=O)C1=C(C)CCCC1(C)C BGTBFNDXYDYBEY-FNORWQNLSA-N 0.000 claims description 3
- 239000005973 Carvone Substances 0.000 claims description 3
- GUUHFMWKWLOQMM-UHFFFAOYSA-N alpha-n-hexylcinnamic aldehyde Natural products CCCCCCC(C=O)=CC1=CC=CC=C1 GUUHFMWKWLOQMM-UHFFFAOYSA-N 0.000 claims description 3
- POIARNZEYGURDG-UHFFFAOYSA-N beta-damascenone Natural products CC=CC(=O)C1=C(C)C=CCC1(C)C POIARNZEYGURDG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 claims description 2
- JRJBVWJSTHECJK-LUAWRHEFSA-N (z)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one Chemical compound CC(=O)C(\C)=C/C1C(C)=CCCC1(C)C JRJBVWJSTHECJK-LUAWRHEFSA-N 0.000 claims description 2
- BTYLJLLMYNHHNC-UHFFFAOYSA-N 1-hydroxy-1-phenylbutan-2-one Chemical compound CCC(=O)C(O)C1=CC=CC=C1 BTYLJLLMYNHHNC-UHFFFAOYSA-N 0.000 claims description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 2
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 2
- 239000006001 Methyl nonyl ketone Substances 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229940058302 antinematodal agent piperazine and derivative Drugs 0.000 claims description 2
- YJSUCBQWLKRPDL-UHFFFAOYSA-N isocyclocitral Chemical compound CC1CC(C)=CC(C)C1C=O YJSUCBQWLKRPDL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 claims description 2
- CRIGTVCBMUKRSL-FNORWQNLSA-N 1-(2,6,6-trimethylcyclohex-2-en-1-yl)but-2-enone Chemical compound C\C=C\C(=O)C1C(C)=CCCC1(C)C CRIGTVCBMUKRSL-FNORWQNLSA-N 0.000 claims 1
- MZZRKEIUNOYYDF-UHFFFAOYSA-N 2,4-dimethylcyclohex-3-ene-1-carbaldehyde Chemical compound CC1C=C(C)CCC1C=O MZZRKEIUNOYYDF-UHFFFAOYSA-N 0.000 claims 1
- 150000003141 primary amines Chemical class 0.000 claims 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 abstract description 4
- 239000003599 detergent Substances 0.000 description 53
- 239000007844 bleaching agent Substances 0.000 description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 45
- 239000011734 sodium Substances 0.000 description 42
- 239000002253 acid Substances 0.000 description 41
- 239000002245 particle Substances 0.000 description 36
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 35
- 239000007795 chemical reaction product Substances 0.000 description 35
- 235000019645 odor Nutrition 0.000 description 35
- 229910052708 sodium Inorganic materials 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 30
- 239000004365 Protease Substances 0.000 description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 26
- 239000010457 zeolite Substances 0.000 description 25
- 239000004367 Lipase Substances 0.000 description 24
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 24
- 239000004382 Amylase Substances 0.000 description 23
- 108010065511 Amylases Proteins 0.000 description 23
- 102000013142 Amylases Human genes 0.000 description 23
- 102000004190 Enzymes Human genes 0.000 description 23
- 108090000790 Enzymes Proteins 0.000 description 23
- 235000019418 amylase Nutrition 0.000 description 23
- 229940088598 enzyme Drugs 0.000 description 23
- 239000000047 product Substances 0.000 description 23
- 108091005804 Peptidases Proteins 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 22
- 102000004882 Lipase Human genes 0.000 description 21
- 108090001060 Lipase Proteins 0.000 description 21
- 229910021536 Zeolite Inorganic materials 0.000 description 21
- 235000019421 lipase Nutrition 0.000 description 21
- 239000007921 spray Substances 0.000 description 20
- 108010059892 Cellulase Proteins 0.000 description 19
- 239000012190 activator Substances 0.000 description 19
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 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 18
- 229940106157 cellulase Drugs 0.000 description 17
- 150000003839 salts Chemical group 0.000 description 17
- 239000002689 soil Substances 0.000 description 17
- 102000004373 Actin-related protein 2 Human genes 0.000 description 16
- 108090000963 Actin-related protein 2 Proteins 0.000 description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 150000001413 amino acids Chemical class 0.000 description 15
- 229960004106 citric acid Drugs 0.000 description 15
- 235000015165 citric acid Nutrition 0.000 description 15
- 238000009472 formulation Methods 0.000 description 15
- 235000001014 amino acid Nutrition 0.000 description 14
- 229940024606 amino acid Drugs 0.000 description 14
- 239000008394 flocculating agent Substances 0.000 description 14
- 235000019832 sodium triphosphate Nutrition 0.000 description 14
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 13
- 239000000654 additive Substances 0.000 description 13
- 229920001296 polysiloxane Polymers 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 101710101449 Alpha-centractin Proteins 0.000 description 12
- 102100040399 C->U-editing enzyme APOBEC-2 Human genes 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 12
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 11
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 11
- 239000002738 chelating agent Substances 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- 239000008187 granular material Substances 0.000 description 11
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 102100038776 ADP-ribosylation factor-related protein 1 Human genes 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 10
- 239000002518 antifoaming agent Substances 0.000 description 10
- 238000004061 bleaching Methods 0.000 description 10
- 150000005323 carbonate salts Chemical class 0.000 description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 10
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 10
- 239000004472 Lysine Substances 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 230000003111 delayed effect Effects 0.000 description 9
- 229910021647 smectite Inorganic materials 0.000 description 9
- 102000003741 Actin-related protein 3 Human genes 0.000 description 8
- 108090000104 Actin-related protein 3 Proteins 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 230000000875 corresponding effect Effects 0.000 description 8
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 8
- 229920005646 polycarboxylate Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000003780 insertion Methods 0.000 description 7
- 230000037431 insertion Effects 0.000 description 7
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- CRIGTVCBMUKRSL-ALCCZGGFSA-N α-damascone Chemical compound C\C=C/C(=O)C1C(C)=CCCC1(C)C CRIGTVCBMUKRSL-ALCCZGGFSA-N 0.000 description 7
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000002262 Schiff base Substances 0.000 description 6
- 150000004753 Schiff bases Chemical class 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
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- ALHUZKCOMYUFRB-UHFFFAOYSA-N muskone Natural products CC1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ZRXJXIVOMZDPKQ-UHFFFAOYSA-N phenyl 6-(nonanoylamino)hexanoate Chemical compound CCCCCCCCC(=O)NCCCCCC(=O)OC1=CC=CC=C1 ZRXJXIVOMZDPKQ-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000724 poly(L-arginine) polymer Polymers 0.000 description 1
- 108010011110 polyarginine Proteins 0.000 description 1
- 229920002704 polyhistidine Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 239000012898 sample dilution Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- GIPRGFRQMWSHAK-UHFFFAOYSA-M sodium;2-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=CC=C1S([O-])(=O)=O GIPRGFRQMWSHAK-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- OYNITBPACPPTCI-UHFFFAOYSA-M sodium;boric acid;hydrogen carbonate Chemical compound [Na+].OB(O)O.OC([O-])=O OYNITBPACPPTCI-UHFFFAOYSA-M 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- DKZBBWMURDFHNE-UHFFFAOYSA-N trans-coniferylaldehyde Natural products COC1=CC(C=CC=O)=CC=C1O DKZBBWMURDFHNE-UHFFFAOYSA-N 0.000 description 1
- XMLSXPIVAXONDL-UHFFFAOYSA-N trans-jasmone Natural products CCC=CCC1=C(C)CCC1=O XMLSXPIVAXONDL-UHFFFAOYSA-N 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- USPJNXWHVJTDJW-UHFFFAOYSA-N tricyclo[5.2.1.02,6]decane-3-carbaldehyde Chemical compound C1CC2C3C(C=O)CCC3C1C2 USPJNXWHVJTDJW-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 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
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- OJYLAHXKWMRDGS-UHFFFAOYSA-N zingerone Chemical compound COC1=CC(CCC(C)=O)=CC=C1O OJYLAHXKWMRDGS-UHFFFAOYSA-N 0.000 description 1
- FUQAYSQLAOJBBC-PAPYEOQZSA-N β-caryophyllene alcohol Chemical compound C1C[C@](C2)(C)CCC[C@]2(O)[C@H]2CC(C)(C)[C@@H]21 FUQAYSQLAOJBBC-PAPYEOQZSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/507—Compounds releasing perfumes by thermal or chemical activation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Fats And Perfumes (AREA)
Abstract
The present invention relates to a laundry and cleaning composition comprisi ng a detersive ingredient and a product of reaction between an amino functional polymer comprising at least one primary and/or secondary amine group, and a perfume component. By the present invention, there is obtained a release of the perfume component over a longer period of time than by the use of the perfume itself.
Description
LAUNDRY AND CLEANING COMPOSITIONS
Field of the invention The present invention relates to laundry and cleanings compositions comprising a product of reaction between an amino functional polymer comprising at least one primary and/or secondary and/or secondary amine group, and a perfume component, in particular aldehyde or ketone perfumes.
Backgiround of the invention Laundry and cleaning products are well-known in the art. However, consumer acceptance of laundry and cleaning products is determined not only by the performance achieved with these products but also by the aesthetics associated therewith. The perfume components are therefore .an important aspect of the successful formulation of such commercial products.
It is also desired by consumers for laundered fabrics to maintain the pleasing fragrance over time. Indeed, perfume additives make laundry compositions more aesthetically pleasing to the consumer, and in some cases the perfume imparts a pleasant fragrance to fabrics treated therewith. However, the amount of perfume carried-over from an aqueous laundry bath onto fabrics is often marginal and does not last long on the fabric. Furthermore, fragrance materials are often very costly and their inefficient use in Laundry and cleaning compositions and ineffective delivery to fabrics results in a very high cost to both consumers and laundry and cleaning manufacturers. Industry, therefore, continues to seek with urgency for more efficient and effective fragrance delivery in laundry and cleaning products, especially for improvement in the provision of long-lasting fragrance to the fabrics.
One solution is to use carrier mechanisms for perfume delivery, such as by encapsulation. This is taught in the prior art and described in U.S.
5,188,753.
Still another solution is to formulate compounds whiclh provide a delayed release of the perfume over a longer period of time than by the use of the perfume itself.
Disclosure of such compounds may be found in WO 95/04809, WO 95!08976 and co-pending application EP 95303762.9.
However, notwithstanding the advances in the art, there is still a need for a compound which provides a delayed release of the pertume component.
That need is even more acute for perfume ingredients which are characteristic of the fresh notes, namely the aldehydes and ketones perfume ingredients. Indeed, whilst these provide a fresh fragrance, these perfumes are also very volatile and have a low substantivity on the surface to be treated like fabrics.
Accordingly, it is a further object of the invention to provide a laundry and cleaning composition comprising a perfume component which provides a fresh fragrance and is substantive to the treated surface.
The Applicant has now found that specific reaction products of an amino functional polymer comprising at least one primary and/or secondary amine group with an active aldehyde or ketone; such as imines compounds, also provide a delayed release of the active such as a perlfume.
/mine compounds are known in the art under the name of Schiff bases which is the condensation of an aldehyde perfume ingredient with an anthranilate. A
typical description can be found in US 4853369. By means of this compound, the aldehyde perfume is made substantive to the fabrics. However, a problem encountered with these schiff bases is that the me~thyianthranilate compound also exhibits a strong scent, which as a result produces a mixture of fragrances, thereby reducing or even inhibiting the aldehyde and/or ketone fragrance perception.
To achieve such perfume composition with comparable aldehyde or ketones fresh notes whilst still having satisfactory fabric substantivity, perfumers have WO 00102982 PCTlUS99/15678 formulated around the composition. For example, by having a carrier or encapsulating material for such notes such as with cyclodextrin, zeolites or starch.
Still another solution is the use of a glucosamine as described in JP
09040687.
However, this compound has been found to give a very low stability in the wash/cileaning process. As a result, insufficient perfume residuality on the treated fabric and/or hard surface has been found with these giucosamine compounds.
A further solution is described in Chemical release control, Kamogawa et AL, J.
Poly. Sci. Polym. Chem. Ed. Vol 20, 3121 (1982) which describe the use of amino styrene compounds condensed with aidehydes perfumes, whereby the release of the perfume is triggered by means of copolymerisation or acidification of the compound. Its use in laundry and cleaning product is however not mentioned.
The Applicant has now found that a reaction product of an amino functional polymer comprising at least one primary and/or secondary amine group, and a perfume component also fulfill such a need.
Another advantage of the compounds of the invention is their ease of manufacture rendering their use most desirable.
Summary of the invention The present invention relates to a laundry and cleaniing composition comprising a detersive ingredient and a product of reaction between an amino functional polymer comprising at least one primary and/or secondary amine group and a perfume component selected from ketone, aldehyde, and mixtures thereof, characterised in that said amino functional polymer has an Odour Intensity Index of less than that of a 1 % solution of methylanthranilate in dipropyiene glycol, and the product of reaction a ~ry Surface Odour Index of amore than 5.
Field of the invention The present invention relates to laundry and cleanings compositions comprising a product of reaction between an amino functional polymer comprising at least one primary and/or secondary and/or secondary amine group, and a perfume component, in particular aldehyde or ketone perfumes.
Backgiround of the invention Laundry and cleaning products are well-known in the art. However, consumer acceptance of laundry and cleaning products is determined not only by the performance achieved with these products but also by the aesthetics associated therewith. The perfume components are therefore .an important aspect of the successful formulation of such commercial products.
It is also desired by consumers for laundered fabrics to maintain the pleasing fragrance over time. Indeed, perfume additives make laundry compositions more aesthetically pleasing to the consumer, and in some cases the perfume imparts a pleasant fragrance to fabrics treated therewith. However, the amount of perfume carried-over from an aqueous laundry bath onto fabrics is often marginal and does not last long on the fabric. Furthermore, fragrance materials are often very costly and their inefficient use in Laundry and cleaning compositions and ineffective delivery to fabrics results in a very high cost to both consumers and laundry and cleaning manufacturers. Industry, therefore, continues to seek with urgency for more efficient and effective fragrance delivery in laundry and cleaning products, especially for improvement in the provision of long-lasting fragrance to the fabrics.
One solution is to use carrier mechanisms for perfume delivery, such as by encapsulation. This is taught in the prior art and described in U.S.
5,188,753.
Still another solution is to formulate compounds whiclh provide a delayed release of the perfume over a longer period of time than by the use of the perfume itself.
Disclosure of such compounds may be found in WO 95/04809, WO 95!08976 and co-pending application EP 95303762.9.
However, notwithstanding the advances in the art, there is still a need for a compound which provides a delayed release of the pertume component.
That need is even more acute for perfume ingredients which are characteristic of the fresh notes, namely the aldehydes and ketones perfume ingredients. Indeed, whilst these provide a fresh fragrance, these perfumes are also very volatile and have a low substantivity on the surface to be treated like fabrics.
Accordingly, it is a further object of the invention to provide a laundry and cleaning composition comprising a perfume component which provides a fresh fragrance and is substantive to the treated surface.
The Applicant has now found that specific reaction products of an amino functional polymer comprising at least one primary and/or secondary amine group with an active aldehyde or ketone; such as imines compounds, also provide a delayed release of the active such as a perlfume.
/mine compounds are known in the art under the name of Schiff bases which is the condensation of an aldehyde perfume ingredient with an anthranilate. A
typical description can be found in US 4853369. By means of this compound, the aldehyde perfume is made substantive to the fabrics. However, a problem encountered with these schiff bases is that the me~thyianthranilate compound also exhibits a strong scent, which as a result produces a mixture of fragrances, thereby reducing or even inhibiting the aldehyde and/or ketone fragrance perception.
To achieve such perfume composition with comparable aldehyde or ketones fresh notes whilst still having satisfactory fabric substantivity, perfumers have WO 00102982 PCTlUS99/15678 formulated around the composition. For example, by having a carrier or encapsulating material for such notes such as with cyclodextrin, zeolites or starch.
Still another solution is the use of a glucosamine as described in JP
09040687.
However, this compound has been found to give a very low stability in the wash/cileaning process. As a result, insufficient perfume residuality on the treated fabric and/or hard surface has been found with these giucosamine compounds.
A further solution is described in Chemical release control, Kamogawa et AL, J.
Poly. Sci. Polym. Chem. Ed. Vol 20, 3121 (1982) which describe the use of amino styrene compounds condensed with aidehydes perfumes, whereby the release of the perfume is triggered by means of copolymerisation or acidification of the compound. Its use in laundry and cleaning product is however not mentioned.
The Applicant has now found that a reaction product of an amino functional polymer comprising at least one primary and/or secondary amine group, and a perfume component also fulfill such a need.
Another advantage of the compounds of the invention is their ease of manufacture rendering their use most desirable.
Summary of the invention The present invention relates to a laundry and cleaniing composition comprising a detersive ingredient and a product of reaction between an amino functional polymer comprising at least one primary and/or secondary amine group and a perfume component selected from ketone, aldehyde, and mixtures thereof, characterised in that said amino functional polymer has an Odour Intensity Index of less than that of a 1 % solution of methylanthranilate in dipropyiene glycol, and the product of reaction a ~ry Surface Odour Index of amore than 5.
In a further aspect of the invention, there is provided a method of delivering residual fragrance to a surface by means of the compound or composition of the invention.
Detailed description of the invention I-Product of reaction between an amino functional polymer and a perfume component An essential component of the invention is a product of reaction an amino functional polymer comprising at least one primary andlor secondary amine group and a perfume component, so called hereinafter "amine reaction product".
A- Amino functional polymer The amino functional polymer is characterized by an Odour Intensity Index of less than that of a 1 % solution of methylanthranilate in dipropylene glycol.
Odour Intensity Index method By Odour intensity Index, it meant that the pure chemicals were diluted at 1 %
in Dipropylene Glycol, odor-free solvent used in perfumery. This percentage is more representative of usage levels. Smelling strips, or so called "blotters", were dipped and presented to the expert panellist for evaluation. Expert panellists are assessors trained for at least six months in odor grading and whose gradings are checked for accuracy and reproducibility versus a reference on an on-going basis. For each an amino functional polymer, the panellist was presented two blotters: one reference (Me Anthranilate, unknown from the panellist) and the sample. The panellist was asked to rank both smelling strips on the 0-5 odor intensity scale, 0 being no odor detected, 5 being very strong odor present.
Results:
The following represents Odour Intensity Index of an amino functional poiymer suitable for use in the present invention and according to the above procedure.
In each case, numbers are arithmetic averages among 5 expert panellists and the results are statistically significantly different at 95% confidence level:
Methylanthraniiate 1 % (reference) 3.4 1,4-bis-(3-aminopropyl) piperazine (BNPP) 1% 1.0 A general structure for the amino functional polymer containing at least one primary amine group of the present invention, is as follows:
(NH2)n - [B]
wherein n is an index of at least 1 and B is the ~>olymer backbone. B can optionally comprise a branching group, C and hence the amino functional polymer is of the following formula:
(NH2)n - [B] - (C]x wherein x >_:0.
Amino functional polymer containing a secondary amine group have a structure similar to the above excepted that the polymer comprises one or more -NH-groups instead of -NH2. Further, the polymer structure may also have one or more of both -NH2 and -NH- groups.
The amino functional polymer of the present invention contains at least one free, unmodified primary andlor secondary amino group attached to the main chain by hydrogen substitution, or by other suitable insertion or substitution by groups referred to as R*. Also suitable is the amino functional polymer comprising an unmodified primary and/or secondary amino group present on side chain(s).
Preferably, the amino functional polymers of the presE:nt invention will comprise several amino groups, more preferably more than 10 amino groups. The amino functional polymers of the present invention will preferably present a molecular weight (M1I1~ ranging from 150 to 2.10EG; more preferably from 400-50,000;
most preferably from 600 to 40,000.
The amino functional polymer can be a linear homo-, co-polymer and optionally branched, grafted andlor cross-linked.
Suitable polymer backbone B for the purpose of the present invention have the following polymer units i (1 ) (2) F (3) -(CH2-CH)x- -( C- H )x- -(CH _ CHZ-O )x -F I
COOHCOOH
wherein x = 2-105 O
I
F=H, - NH2, - COOH, COOK*, -C - CH3, - O-C -CH3,- OH, - CN, - OR*, O
R*
\/ , \/ OH ~~~ ° N-~"O , O \ / N
I
Suitable branching units C for the polymer backbone B are 2,3 or 2,4 or 3,4 substitution _ _ i N ~ C N\
The polymer backbone B can also comprise insertion groups I such as i WO 00102982 PCTlUS99/15678 -O- ~ -O-O- . -O-, -O-~-O- . -RH- -(CH2~
x>_1 R* or H
-C- , -C-N- , -N- ~ 'C-N- . \C =C\
bH O R* or H R or H * ~ or H ' * R or H
R* or H -~-O- ~ O O
-N- ~ " ~ -O-S-O- , -S-Nt-1- ' -S
O O O O
O
\ / ~ O C \ j , O
The arrow indicates substitution in position 2.3 or 4 n -O_C \-/ C~O- -C \ / C- , ~ a -O O O O
The backbone (B) can also contain several insertion groups linked together:
e.g.
\ / \ / . -yCH,)~ C- . -(CH~)WN- \ /
O
wherein x>- 1.
The aminofunctional polymers of the present invention can further comprise substituents R* in the main chain or in the side chain(s). Typically, R*
replaces an hydrogen atom. This R* group can either be linked directly or via a linker group L to the main or side chain. Suitable linker groups L are the above mentioned insertion groups I.
R* groups are C1 to C22 alkyl, alkenyl, alkylbenzene chain andlor their corresponding substituted derivatives. Such corresponding substituted derivatives include alicyclic, aromatic, heteroaromatic or heterocyciic systems, either inserted in the main chain or incorporated by a substitution of an H
atom in the main chain; an insertion group E in the main chain, as defined herein above and/or an end group E as defined below.
Further, the polymer backbone B and R* encompass end groups E. Typically end groups E can be an H, NH2 groups, an aromatic, alicyclic, heteroaromatic or heterocyclic group including mono-, di-, oligo-, poly-sa~ccharides R* ~ CH
-OH, -OR*.. -NH,. -~( , -C-N-R* or H ~ -N -~ O ' R* or H I
R* or H CH
-S03H, -OS03H, -COOH.-COOK*.
_ I
\ / ~ ~ O ' ~ ~ H
CH3 CH,-CH,-OH
~N=CH3 ' X_~yCH3 ~ X=~N-CH,-CH_.,-OH . -C-OCH,-CH,-N+(CH3)3 CH3 X CH,-CH.,-OH CH3 -wherein Y-= is an anion like C1-,Br ,SO;~''' En addition, the R* group can also be modified via substitution of one or more H
atoms. Said substitution can either be an end group E: or an insertion group I
as defined above, where the insertion group is terminated by a H, E or R* group .
Preferred examples of suitable amino-functional polymers for use in the present invention are selected from the polyvinylamines, derivatives thereof, copolymer thereof, aikylene polyamine, polyaminoacid and copolymer thereof, cross-linked poiyaminoacids, amino substituted polyvinylalcohof, polyoxyethylene bis amine or bis. aminoalkyl, aminoalkyl piperazine and derivatives, N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA), and mixtures thereof.
Polyamino acid is one suitable and preferred class of amino-functional polymer.
Polyaminoacids are compounds which are made up of amino acids or chemicaily modified amino acids. They can contain alanine, serine, aspartic acid, arginine, valine, threonine, glutamic acid, leucine, cysteine, histidine, lysine, isoleucine, tyrosine, asparagine, methionine, proiine, tryptophan, phenylalanine, glutamine, glycine or mixtures thereof. In chemically modified amino acids, the amine or acidic function of the amino acid has reacted with a chemical reagent. This is often done to protect these chemical amine and acid functions of the amino acid in a subsequent reaction or to give special properties to the amino acids, like improved solubility. Examples of such chemical modifications are benzyloxycarbonyl, aminobutyric acid, butyl ester, pyroglutamic acid. More examples of common modifications of amino acids and small amino acid fragments can be found in the Bachem, 1996, Peptides and Biochemicals Catalog.
Preferred polyamino acids are polylysines, polyarginine, polygiutamine, poiyasparagine, polyhistidine, polytryptophane ar mixtures thereof. Most preferred are polylysines or poiyamino acids where more than 50% of the amino acids are lysine, since the primary amine function in the side chain of the lysine is the most reactive amine of all amino acids.
The preferred polyamino acid has a molecular weight of 500 to 10.000.000, more preferably between 5,000 and 750.000.
The polyamino acid can be cross linked. The cross linking can be obtained for example by condensation of the amine group in the side chain of the amino acid like lysine with the carboxyl function on the amino acid or with protein cross linkers like PEG derivatives. The cross linked polyamino acids still need to have free primary andlor secondary amino groups left for reaction with the active ingredient.
The preferred cross linked poiyamino acid has a molecular weight of 20.000 to 10.000.000, more preferably between 200.000 and 2.000.000.
The polyamino acid or the amino acid can be co-polymerized with other reagents like for instance with acids, amides, acyl chlorides. More specifically with aminocaproic acid, adipic acid, ethylhexanoic acid, caproiactam or mixture thereof. The molar ratio used in these copolymers ranges from 1:1 (reagent/
amino acid (lysine)) to 1:20, more preferably from 1:1 to 1:10.
The polyamino acid like pofylysine can be partially ethoxylated.
Examples and supply of polyaminoacids containing lysine, arginine, giutamime, asparagine are given in the Bachem 1996, Peptides and Biochemicals catalog.
The polyaminoacid can be obtained before reaction with the active ingredient, under a salt form. For example polylysine can be supplied as polylysine hydrobromide. Polylysine hydrobromide is commercially available from Sigma, Applichem, Bachem and Fluka.
Examples of suitable amino functional polymers containing at least one primary andlor secondary amine group for the purpose of the present invention are - Polyvinylamine with a MW of about 300-2.10Efi;
- Polyvinyiamine aikoxylated with a MW of about 600, 1200 or 3000 and an ethoxylation degree of 0.5;
- Polyvinylamine vinyialcohol - molar ratio 2:1, pofyvinylaminevinyiformarnide -molar ratio 1:2 and polyvinylamine vinyiformamide-molar ratio 2:1;
- Triethylenetetramine, diethylenetriamine, tetraethylenepentamine;
- Bis-aminopropylpiperazine;
Polyamino acid (L-lysine l lauric acid in a molar ratio of 10/1 ), Poiyamino acid (L-lysine I aminocaproic acid l adipic acid in a molar ratio of 5/511 ), ), Poiyamino acid (L-lysine / aminocaproic acid /ethylhexanoic acid in a molar ratio of 5/3/1 ) Poiyamino acid (polylysine-cocaprolactam); Polylys~ine hydrobromide, cross-linked polylysine, - amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
- polyoxyethylene bis [amine] available from e.g. Sigma;
- polyoxyethyiene bis [6-aminohexyl] available from e.g. Sigma;
- N,N'-bis-(3-aminopropyi)-1,3-propanediamine linear or branched (TPTA); and - 1,4-bis-(3-aminopropyl) piperazine {BNPP).
Preferred amino functional polymers containing at least one primary and/or secondary amine group are - polyvinylamines with a MW ranging from 600, 1200, 3K, 20K, 2bK or 50K;
- amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
polyoxyethylene bis [amine] available from e.g. Sigma;
- polyoxyethylene bis [fi-aminohexyl] available from e..g. Sigma;
- N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA);
- 1,4-bis-(3-aminopropyl) piperazine (BNPP);
- Polylysine hydrobromide;
cross-linked polylysine.
Furthermore, such amino functional polymers comprising at least one primary and/or secondary amine group and the amine reaction product provide fabric appearance benefits, in particular color care and protection against fabric wear.
Indeed, the appearance of fabrics, e.g., clothing, bedding, household fabrics like table linens is one of the area of concern to consumers. Indeed, upon typical consumer's uses of the fabrics such as wearing, washing, rinsing andlor tumble-drying of fabrics, a loss in the fabric appearance; which can be at least partly due to loss of color fidelity and color definition, is observed. Such a problem of color loss is even more acute after multiwash cycles. It has been found that the compositions of the present invention provide improved fabric appearance and protection against fabric wear and improved color care to laundered fabrics, especially after muitiwash cycles.
Therefore, the compositions of the present invention can provide simultaneously fabric care and long lasting perfume benefits.
B-Perfume Preferably, for the above mentioned compounds, by perfume ketone or aldehyde, it is meant any chain containing at least 1 carbon atom, preferably at least 5 carbon atoms.
A typical disclosure of suitable ketone and/or aldehydes, traditionally used in perfumery, can be found in "perfume and Flavor Chemicals", Vol. I and II, S.
Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5.
Perfume ketones components include components having odoriferous properties.
Preferably, for the above mentioned compounds, the perfume ketone is selected for its odor character from buccoxime; iso jasmone; methyl beta naphthyl ketone; musk indanone; tonaiid/musk plus; Alpha-Damascone, Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose, Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-lonone, Beta-lonone, Gamma-Methyl so-callecl lonone, Fleuramone, Dihydrojasrnone. Cis-Jasmone, lso-E-Super, Methyl- Cedrenyl-ketone or Methyl-Cedrylone, Acetophenone, Methyl-AcetophE:none, Para-Methoxy-Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-Acetone, Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery Ketone~ or Livescone, 6-Isopropyidecahydro-2-naphtone, Dimethyl-Octenon~:, Freskomenthe, 4-(1-Ethoxyvinyl)-3,3,5,5,-tetramethy(-Cyclohexanone, Methyl-Heptenone, 2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)-cyclopentanone, 1-(p-Menthen-6(2}-yl)-1-propanone, 4-(4-Hydroxy-3-methoxyphenyl)-2-butanone, 2-Acetyl-3,3-Dimethyl-Norbornane, 6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-C)amascol, Dulcinyl or Cassione, Gelsone, Hexalon, lsocyciemone E, Methyl Cyclocitrone, Methyl-Lavender-Ketone, Orivon, Para-tertiary-Butyl-Cyclohexanone, Verdone, Delphone, Muscone, Neobutenone, Plicatone, Veloutone, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Tetrameran, Undecaiactone and Gamma undecalactone.
For the above mentioned compounds, the more preferred ketones are selected for its odor character from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-ionone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof.
Perfume aldehyde components include components having odoriferous properties.
Preferably, for the above mentioned compounds, the perfume aidehyde is selected for its odor character from adoxal; anisic aidE:hyde; cymai; ethyl vanillin;
florhydral; helionai: heliotropin; hydroxycitronellai; koavone; lauric aldehyde;
lyral; methyl nonyl acetaldehyde; P. T, bucinal; phenyl acetaldehyde;
undecylenic aidehyde; vanillin; 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amyl cinnamic aldehyde, 4-methoxybenzaidehyde, benzaldehyde, 3-(4-tert butylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyf propanal, 2-methyl-4-(2,6,6-trimethyl-2(1)-cyciohexen-1-yl) butanal, 3-phenyl-2-propenal, cis-/traps-3,7-dimethyi-2,6-octadien-1-al, 3,7-dimethyi-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy] acetaldehyde, 4-isopropylbenzyaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyciohexen-1-carboxaidehyde, 2-methyl-3-(isopropyiphenyl)propanai, 1-decanal; decyl aldehyde, 2,6-dimethyi-5-heptenal, 4-(tricycto[5.2.1.0(2,6)]-decyiidene-8)-butanal, octahydro-4,7-methano-1 H-indenecarboxaldehyde, 3-ethoxy-4-hydroxy benzaldehyde, para-ethyl-alpha, alpha-dimethyi hydrocinnamaldehyde, alpha-methyl-3,4-(methyienedioxy)-hydrocinnamaidehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde, m-cymene-7-carboxaidehyde, alpha-methyl phenyl acetaldehyde, 7-hydroxy-3,7-dimethyl octanai, Undecenal, 2,4,6-trimethyl-3-cyciohexene-'I-carboxaldehyde, 4-{3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaidehyde, 1-dodecanal, 2,4-dimethyl cyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methyl pentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal, dihydrocinnamic aldehyde, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5 or Ei methoxy0hexahydro-4,7-methanoindan-1 or 2- carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al, 4-hydroxy-3-methoxy benzaldehyde, 1-methyl-3-{4-methylpentyl)-3-cycihexenecarboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, traps-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde; 4-methylphenylacetaldehyde, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-cyclohexene carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dime~thyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al), hexahydro-4,7-methanoindan-1-carboxaldehyde, 2-methyl octanal, alpha-methyl-4.-(1-methyl ethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinene-2-propionaldehyde, para methyl phenoxy acetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethyl hexanal, Hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicycio[2.2.1]-hept-5-ene-2-carbaldehyde, 9-decenal, 3-nnethyl-5-phenyl-1-pentanal, rnethylnonyl acetaldehyde, hexanal, traps-2-hexenal, 1-p-menthene-q-carboxaldehyde and mixtures thereof.
More preferred aldehydes are selected for its odor character from 1-decanat, benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-1-carbaxaldehyde;
cis/traps-3,7-dimethyl-2,6-octadien-1-al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, alpha-n-hexyi cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal, traps-2-hexenal, and mixture thereof.
In the above list of perfume ingredients, sorne~ are commercial names conventionally known to one skilled in the art, and also includes isomers.
Such isomers are also suitable for use in the present invention.
In another embodiment, especially suitable for the purpose of the present invention are the perfume compounds, preferably the perfume ketoses or aldehydes, characterized by having a low Odor Detection Threshold. Such Odor Detection Threshold (ODT) should be lower than 1 ppm, preferably lower than 10ppb - measured at controlled Gas Chromatography {GC) conditions such as described here below. This parameter refers to the value commonly used in the perfumery arts and which is the lowest concentration at which significant detection takes place that some odorous material is present.
Please refer for example in "Compilation of Odor and Tasi:e Threshold Value Data (ASTM DS 48 A)", edited by F. A. Fazzalari, International Business Machines, Hopwell Junction, NY and in Catkin et al., Perfumery, Practice and Principles, John Willey & Sons, Inc., page 243 et seq (1994). For the purpose of the present invention, the Odor Detection Threshold is measured according to the following method The gas chromatograph is characterized to determine the exact volume of material injected by the syringe, the precise spfit ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution. The air flow rate is accurately measured and, assuming the duration of a human inhalation to last 0.02 minutes, the sampled volume is calculated. Since the precise concentration at the detector at any paint in time is known, the mass per volume inhaled is known and hence the concentration of material. To determine the ODT of a perfume material, solutions are delivered to the sniff port at the back-calculated concentration. A panelist sniffs the GC effluent and identifies the retention time when odor is noticed.
The average over all panelists determines the threshold of noticeability. The necessary amount of analyte is injected onto the column to achieve a certain concentration, such as 10 ppb, at the detector. Typical gas chromatograph parameters for determining odor detection thresholds are listed below.
GC: 5890 Series Il with FID detector 7673 Autosampler Column: J&W Scientific DB-1 Length 30 meters ID 0.25 mm film thickness 1 micron Method:
Split Injection: 17/1 split ratio Autosampler: 1.13 microliters per injection Column Flow: 1.10 mUminute Air Flow: 345 mUminute Inlet Temp. 245°C
Detector Temp. 285°C
Temperature Information Initial Temperature: 50°C
Rate: 5C/minute Final Temperature: 280°C
Final Time: 6 minutes Leading assumptions: 0.02 minutes per sniff GC air adds to sample dilution Examples of such preferred perfume components are those selected from : 2-methyl-2-(para-iso-propyiphenyl)-propionaldehyde, 1-(2,6,6-trimethyl-2-cyclohexan-1-yl)-2-buten-1-one andlor para-methoxy-acetophenone. Even more preferred are the following compounds having an ODT <_ l0ppb measured with the method described above : undecylenic aldehydE~, undecalactone gamma, heliotropin, dodecalactone gamma, p-anisic aldehyde, pats hydroxy-phenyl-butanone, cymal, benzyl acetone, ionone alpha, p.t.bucinai, damascenone, ionone beta and methyl-nonyl ketone.
Typically the level of perfume is of from 10 to 90%, preferably from 30 to 85%, more preferably from 45 to 80% by weight of the amine reaction product.
Preferred amine reaction products are those resulting from the reaction of polyaminoacid like Polylysine, BNPP, or TPTA with one or more of the following Alpha Damascone, Delta Damascone, Canrone, fiedione, Florhydral, Lilial, Heliotropine, Gamma-Methyl-lonone and 2,~4-dimethyl-3-cyclohexen-1-carboxaldehyde, and mixture thereof.
Most preferred amine reaction products are those from the reaction of BNPP or TPTA with Alpha and Delta Damascone.
Process Preparation of the component is made as follows in the Synthesis Examples. In general, the nitrogen analogs of ketones and aldehyd~es are called azornethines, Schiff bases or the more preferred name imines. These imines can easily be prepared by condensation of primary amines and carbonyl compounds by elimination of water.
A typical reaction profile is as follows:
R,yR ' HEN.-R" ~- R--C-NH-R"
I
R' R
v /c=N-R" + HBO
R' a,~i-Unsaturated ketones do not only condense with amines to form imines, but can also undergo a competitive 1,4-addition to form ~3-;aminoketones.
WO 00!02982 PCT/US99/15678 R"
O
R-CH=CH-IC-R' + H N-R" ---~ f H O
R-CH-CH-C-R' By means of this simple method, compound and composition containing said compounds are made which achieve a delayed release of the active ingredient.
As can be observed, the perfume ingredient preferably needs to be present in equimolar amount to the amine function so as to enable the reaction to take place and provide the resulting amine reaction product. Of course, higher amount are not excluded and even preferred when the amine compound comprises more than one amine function.
Mechanism of release By the present invention, a delayed release of a perfume ingredient, i.e.
ketone or aldehyde is obtained. Not to be bound by theory, the release is believed to occur by the following mechanisms:
For imine compounds, the perfume components are released upon breaking down of the imine bond, leading to the release of the perfume component and of the primary amine compound. This can be achieved by either hydrolysis, photochemical cleavage, oxidative cleavage, or enzymatic cleavage.
For ~-aminoketone compounds, treatment with air moisture andlor water successfully releases the perfume component and the amine compound.
However, other means of release are not excluded like hydrolysis, photochemical cleavage, oxidative cleavage, or enzymatic cleavage.
Still other means of release for imine as well as ~-aminoketone compounds can be considered such as by the steaming step of ironing the treated fabric, tumble-drying, and/or wearing.
Laundry and cleaning compositions The present invention include both laundry and cleaning compositions which are typically used for Laundering fabrics and cleanings hard surfaces such as dishware, floors, bathrooms, toilet, kitchen and other surfaces in need of a delayed release of perfume ketone andlor aldehyde. Accordingly, by laundry and cleaning compositions, these are to be understood to include not only detergent compositions which provide fabric cleaning benefits, but also compositions such as hard surface cleaning which provide hard surface cleaning benefit.
Preferred are those laundry compositions which result in contacting the compound of the invention with fabric.
Preferably, the amine reaction products) which is incorporated into such laundry and cleaning compositions provides a dry surface Odour Index of more than 5 preferably at least '! 0.
By Dry Surface Odour Index, it is meant that the amine reaction products) provides a Delta of more than 5, wherein Delta is the difference between the Odour Index of the dry surface treated with amine reaction products) and the Odour Index of the dry surface treated with only the perfume raw material.
Measurement method of Dry Surface Odour Index:
For the above Dry Surface Odour Index, the amine reaction product suitable for use in the present invention needs to fulfill at least one of the following two tests.
Preferred amine reaction product suitable for use in the present invention fulfill both test.
1)-For fabric surface Product preparation:
The amine reaction product is added to the unperfumed product base.
The unperfumed product base, wherein the abreviations are as defined herein after for the examples, is as follows:
Composition . % by weight ~.AS 1 s NaSKS-6 TAED 2.4 Carbonate 1 Sodium Carbonate 1 HEDP 0.4 SRP1 0.2 Photobleach 0.013 Citric acid 1.0 Protease 0.3 Lipase 0.1 Cellulase 0.1 Amylase 0.3 Zeolilte 3.0 TFAA 3.0 QAS1 2.5 Silicone antifoam 1.0 Misclminors to balance to 100%
Levels of amine reaction product are selected so as to obtain an odour grade on the dry fabric of at least 20. After careful mixing, by shaking the container in case of a liquid, with a spatula in case of a powder, tlhe product is allowed to sit for 24 hrs.
Washing process:
The resulting product is added into the washing machine in the dosage and in the dispenser appropriate for its category. The quantity corresponds to recommended dosages made for the corresponding market products: typically between 70 and 150 g for a detergent powder or liquid via current dosing device like granulette, or ariellette. The load is composed of four bath towels (170g) using a Mieie W830 washing machine at 40°C short cycle, water input :15°Hardness at a temperature of 10-18°C, and full spin of 1200rpm.
The same process is applied for the corresponding free perfume ingredient in consideration and is used as the reference. Dosages, fabric toads and washing cycles for the reference and the sample are identical.
Drying Process:
Within two hours after the end of the washing cycle, the spinned but still wet fabrics are assessed for their odors using the scale mentioned below.
Afterwards, half of the fabric pieces are hung on a line for 24 hr drying, away from any possible contaminations. Unless specified, this drying takes place indoor. Ambient conditions are at temperature between 18-25C and air moisture between 50-80%. The other half is placed in a tumble drier and undergoes a full "very dry" cycle, i.e. in a Miele, Novotronic T430 set on program white-extra dry (full cycle). Tumble dry fabrics are also assessed on the next day. Fabrics are then stored in opened aluminum bags in an odor free room, and assessed again after 7 days.
Odor Evaluations:
Odor is assessed by expert panellist smelling the fabrics. A 0-100 scale is used for all fabric odor gradings. The grading scale is as follows 100 = extremely strong perfume odor 7a = very strong perfume odor 50 = strong odor 40 = moderate perfume odor = slight perfume odor 20 = weak perfume odor 10 = very weak perfume odor 0 = no odor A difference of more than 5 grades after one day and/or 7 days between the amine reaction product and the perfume raw material is statistically significant. A
difference of 10 grades or more after one day and/or 7 days represents a step-change. In other words, when a difference of grade of more than 5, preferably at least 10 is observed between the amine reaction product and the perfume raw material, after either 1 day or 7 days or both 1 day and 7 days, it can be concluded that the amine reaction product is suitable for use in the present invention, provided that the amine compound fulfill the Odour Intensity Index.
2)-For hard surface:
Product preparation:
The perfume raw material or blend thereof is added and carefully mixed at 0.255% in the unperfumed Hard Surface Cleaner base.
The unperfumed product base, wherein the abreviations ace as defined herein after for the examples, is as follows:
Composition for hard surface test % by weight C12-14 EO 5 2,~
C9-11 EO 5 2.5 ~S 0.8 Na2C03 0,2 Citric acid p.g Caustic acid 0.5 Fatty acid 0,5 SCS 1.5 Water &Misc/Minors to balance to 100%
After mixing and standing for 24 hrs, the homogeneity of the product is checked.
In case of phase separation due to poor solubility of the perfume ingredients) an appropriate amount of Sodium p. Cymene Sulfonate or another solubilising agent is added till a homogeneous solution is obtained.
Cleaning process:
Five grams of this solution are evenly applied on the upper side of a ceramic tile (875 square cm, e.g. from Vileroy-Boch). After 1 minute the tile is rinsed with 1 liter of tap water. The tile is then placed in a vertical position for 3 minutes to allow the rinse water to drip off.
Finally, the tile is placed in a clean and aerated perspex box {38 x 40 x 32 cm) with a removable cover that has a sliding-lid (10 x 10 cm) to allow expert evaluators to smell the interior phase of the box.
The odor in the box is evaluated just after placing the tile in it (fresh reading) and after 1, 2 and 6 hours.
Odor Evaluation:
The grading scale is as follows 50 = very strong odor 40 = strong odor 30 = moderate odor 20 = slight odor = weak odor 0 = no odor Every test includes a blanc (unperfumed Hard Surface Cleaner) and in the case of testing perfume precursor, so-called amine. reaction product the corresponding free perfume ingredient is also included so that the effect of the carrier is adequately measured.
Again as for the Dry surface Odour Index method for fabrics, a difference of more than 5 grades after 1 day andlor 7 days between , the amine reaction product and the perfume raw material is statistically significant. A
difference of 10 grades or more after 1 day andlor 7 days represents a step-change. In other words, when a difference of grade of more than 5, preferably at least 10 is observed between the amine reaction product and t:he perfume raw material, after either 1 day or 7 day or both 1 day and 7 days, it can be concluded that the amine reaction product is suitable for use in the present, provided that the amine compound fulfill the Odour Intensity Index.
The amine reaction product as defined herein before is typically comprised from 0.0001 % to 10%, preferably from 0.001% to 5%, and more preferably from 0.01 % to 2%, by weight of the composition. Mixture, of the compounds may also be used herein.
Incorporation of the amine reaction product in the laundry and cleaning compositions can conveniently be carried out, if necessary, by conventional incorporation means, such as by spray-on, encapsulation like starch encapsulation, e.g. as described in GB1464616, dry addition, or by encapsulation in cyclodextrin. Preferably, the amine reaction product is preformed before incorporation into the laundry and cleaning compositions. In other words, the perfume component and the amino functional polymer of the present invention are first reacted together to obtain tlhe resulting amine reaction product as defined in the present invention and only once formed incorporated into the laundry and cleaning compositions. By be;ing preformed before the incorporation in fully formulated composition, a better control of the compound being made is obtained. Hence, the interaction with perfume composition which may be present in fully formulated composition is avoided as well as side reaction that could occur. Further, by such means of incorporation, efficient control of the yield and purity of the compound is obtained.
Most preferably, when the laundry and cleaning composition comprises a perfume, the amine reaction product is incorporated in the composition separately from the perfume. By this means, the amine reaction product and its subsequent perfume release is more controlled.
Typically the laundry and cleaning composition comprises a detersive ingredient and further optional ingredients as described hereinafter as optional ingredients.
Detersive ingredients Non-limiting examples of surfactants useful herein typically at levels from 1 % to 55%, by weight, include the conventional C11-C1EI alkyl benzene sulfonates ("LAS"} and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the C10-C1g secondary (2,3) alkyl suff,ates of the formula CH3(CH2)x(CHOS03-M+) CH3 and CH3(CH2)y(CHOS03-M+) CH2CH3 where x and (y + 1 ) are integers..of at least 7, preferably ai: least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oley!
sulfate, the C10-C1g alkyl alkoxy sulfates ("AEXS"; especially x up to 7 EO ethoxy sulfates), C10-C1g alkyl alkoxy carboxyiates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C1 g alkyl poiyglycosides and their corresponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C1g alkyl e~thoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C12 alkyl phenol alkoxylates {especially ethoxylates and mixed ethoxylpropoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C10-C~;g amine oxides, cationic surfactants and the like, can also be included in the overall compositions.
The C10-C1g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C1g N-methyiglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C1p-C1g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C1g glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. if high sudsing is desired, the branched-chain C10-C1g soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfaci:ants are listed in standard texts.
Fully formulated laundry and cleaning compositions preferably contain, in addition to the hereinbefore described components, one or more of the following ingredients.
Builders Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1 % builder, preferably from 1 % to 80%. Liquid formulations typically comprise from 5% to 50%, mare typically 5% to 30%, by weight, of detergent builder. Granular formulations typically comprise from 1 % to 80%, more typically from 5% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and aikanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly those having a Si02:Na20 ratio in the range 1.0:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. 4,664,839. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Si05 morphology form of layered silicate. It can be prepared by method such as those described in DE-A-3,417,649 and DE-A-3,74:?,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSix02x+1 ~yH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2SiO~i (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaiine~ earth and alkali metal carbonates as disclosed in DE 2,321,001.
Aluminosilicate builders are useful in the present invention. Aluminosiiicate builders are of great importance in most currently marketed heavy duty granutar detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
Mz/n~(A102)z(Si02)yj~xH20 wherein z and y are integers usually of at least 6, the molar ratio of z to y is in the range from 1.O to 0, and x is an integer from 0 to 264, and M is a Group IA or IIA element. e.g., Na, K, Mg, Ca with valence n.
Useful aluminosilicate ion exchange materials are commercially available.
These aiuminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is ciisciosed in U.S.
3,985,669.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP
and Zeoiite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Na l 2~(A102)12(Si02) 121~xH20 wherein x is from 20 to 30, especially 27. This matssrial is known as Zeolite A.
Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to; a wide variety of poiycarboxylate compounds.
As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylatE~s. Polycarbaxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanoiammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S.
3,128,287, U.S. 3,635,830. See also "TMSITDS" builders of U.S. 4,663,071.
Suitable ether polycarboxylates also include cyclic compounds, particularly aiicyclic compounds, such as those described in U.S. 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypoiycarboxylates, copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid anti nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, pyromeliitic, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite andlor layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the preaent invention are the 3;3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
4,566,984. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in E=P 0,200,263.
Other suitable polycarboxylates are disclosed in U.S 4,144,226 and in U.S.
3,308,067. See also U.S. 3,723,322.
Fatty acids, e.g., C12-C1g monocarboxyfic acids such as oleic acid and/or its salts, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate andlor the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can 1be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripoiyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates {see, for example, U.S. Patents 3,159,581; 3,213,030;3,422,021; 3,400,148 and 3,422,137) can also be used.
WO 00!02982 PCT/US99/15678 Bleaching ComAOUnds - Bleaching Aqents and Bleach Activators The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing .a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from to 30%, more typically from 5% to 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator, The bleaching agents used herein can be any. of the bleaching agents useful for detergent compositions in textile cleaning or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents like hypochiorite bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein. When hypochiorite is used, a highly preferred hypochlorite bleaching component is an alkali metal hypochlorite. Although alkali metal hypochlorites are preferred, other hypochiorite compounds may also be used herein and can be selected from calcium and magnesium hypochlorite. A preferred alkali metal hypochlorite for use herein is sodium hypochlorite.
Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents <~nd salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S 4,483,781, U.S 740,446, EP 0,133,354, and U.S 4,412,934.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S 4,634,551.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1,000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1,250 micrometers.
Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Sofvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution {i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S 4,915,854, and U.S 4,412,934. The nonanoyloxybenzene sulfonate (NOBS), 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate (ISONOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L.
wherein R1 is an alkyl group containing from 6 to '12 carbon atoms, R2 is an alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is any suitable leaving group. A
leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesuifonate, (6-nonanamidacaproyl)oxybenzene sulfonate, (6-decanamido-caproyl)oxybenzenesuifonaite, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723. ,A highly preferred activator of the benzoxazin-type is:
O
II
CEO
~~C o.J
N
Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
s~0 C-CH2-CH2\ 6-O C-CHz-CH2 R C-N~CH2-CH2~CH2 R C-NCH - ~ H
wherein R6 is H or an alkyl, aryl, aikoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimet:hylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolac~am, undecenoyi valerolactam, nonanoyi valeroiactam, 3,5,5-trimethylhexanoyi valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, is:>ued to Sanderson, October 8, 1985; incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agenta are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc andlor aluminum phthalocyanines. See U.S. 4,033,718. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well-known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,246,621, U.S.
5,244,594; U.S. 5,194,416; U.S. 5,114,606; and E:P 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include MnlV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mnlll2 (u-O}1(u-\:
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2_{C104)2, MnlV4(u-O)6(1,4,7-triazacyclononane)4(CI04)4, MnIIIMniV4(u-O)1(u-C)Ac)2_(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)-{OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and ll.S. 5,114,611. The use of manganese with various complex Iigands to enhances bleaching is also reported in the following US Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779;
5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in thie aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundr)r liquor.
Briqhteners The compositions herein can also optionally contaiin from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compasi!tions herein will preferably comprise from 0.001 % to 1 % by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
Rt R
--N H H rl N ~~--N a C=C ~ N--~{~ N
j"-N H H rf --C
R~~ SO;M S03M R~
wherein R1 is selected from aniiino, N-2-bis-hydroxyethyi and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyi-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anifino, R2 is N-2-l:>is-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. Tinopa!-UNPA-GX
is the preferred hydrophilic optical brightener useful in the rinse added compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, they 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 SBM-GX~ by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a canon such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-yi)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX~ by Ciba Geigy Corporation.
Soil Release Agent In the present invention, an optional soil release agent can be added. Typical levels of incorporation in the composition are from 0°~o to 10%, preferably from 0.2% to 5%, of a soil release agent. Preferably, such a soil release agent is a polymer.
Soil Release agents are desirably used in fabric softening compositions of the instant invention. Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions of this invention.
Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophiiize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
If utilized, soil release agents will generally comprise from about 0.01 % to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1 % to about 5%. preferably from about 0.2% to about 3.0%.
The following, all included herein by reference, describe soil release polymers suitable for use in the present invention. U.S. 3,959.230 Hays, issued May 25, 1976; U.S. 3,893,929 Basadur, issued Juiy 8, 1975; U.S. 4,000,093, Nicol, et al., issued December 28, 197fi; U.S. Patent 4.702,857 Gosselink, issued October 27, 1987; U.S. 4,968,451, Scheibel et al., issued November 6; U.S.
4,702,857, Gosselink, issued October 27, 1987; U.S. 4,711,730, Gosselink et al., issued December 8, 1987; U.S. 4,721,580, Gosaelink, issued January 26, 1988; U.S. 4,877,896, Maidonado et al., issued October 31, 1989; U.S.
4,956,447, Gosselink et al., issued September 11, 1990; U.S. 5,415,807 Gosselink et al.; issued May 16. 1995; European Patent Application 0 219 048, published April 22, 1987 by Kud, ef al..
Further suitable soil release agents are described in I,~,S. 4,201,824, Vioiland et al.; U.S. 4,240,918 I_agasse et al.; U.S. 4,525,524 Tung et al.; U.S.
4,579,681, Ruppert et al.; U.S. 4,240,918; U.S. 4,787,989; U.S. 4,525,524; EP 279,134 A, 1988, to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE
2,335,044 to Uniiever N. V., 1974 all incorporated herein by reference.
Commercially available soil release agents include the METOLOSE SM100, METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN
type of material, e.g., SOKALAN HP-22, available from BASF (Germany}, ZELCON 512fi (from Dupont} and MILEASE T (from iCl).
Scum Dispersant In the present invention, the premix can be combined with an optional scum dispersant, other than the soil release agent, and heated to a temperature at or above the melting points) of the components.
The preferred scum dispersants herein are formE:d by highly ethoxylating hydrophobic materials. The hydrophobic material can be a fatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxidE~, quaternary ammonium compound, or the hydrophobic moieties used to form :SOiI release polymers. The preferred scum dispersants are highly ethoxylate:d, e.g., more than 17, preferably more than 25, more preferably more than 4~0, moles of ethylene oxide per molecule on the average, with the poiyethylene~ oxide portion being from 76% to 97%, preferably from 81 % to 94%, of the total molecular weight.
WO 00102982 PCTlUS99/15678 The level of scum dispersant is sufficient to keep the scum at an acceptable, preferably unnoticeable to the consumer, level under the conditions of use, but not enough to adversely affect softening. For some purposes it is desirable that the scum is nonexistent. Depending on the amount of anionic or nonionic detergent, etc., used in the wash cycle of a typical laundering process; the efficiency of the rinsing steps prior to the introduction of the compositions herein, and the water hardness, the amount of anionic or nonionic detergent surfactant and detergency builder (especially phosphates and zeolites) entrapped in the fabric (laundry) will vary. Normally, the minimum amount of scum dispersant should be used to avoid adversely affecting softening properties. Typically scum dispersion requires at least 2%, preferably at least 4% (at least 6% and preferably at least 10% for maximum scum avoidance) based upon the level of softener active. However, at levels of 10% (relative to the softener material) or more, one risks loss of softening efficacy of the product especially when the fabrics contain high proportions of nonionic surfactanf: which has been absorbed during the washing operation.
Preferred scum dispersants are: Brij 700~; Varonic U-250~; Genapol T-500~, Genapol T-800~; Plurafac A-79~; and Neodol 25-50U.
Bactericides Examples of bactericides used in the composition~~ of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-dioi sold by inolex Chemicals, located in Philadelphia, Pennsylvania,. under the trade name Bronopol~, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoiine-3-one sold by Rohm and Haas Company under the trade name Kathon 1 to 1,000 ppm by weight of the agent.
Perfume The present invention can contain any detergent compatible perfume. Suitable perfumes are disclosed in U.S. Pat. 5,500,138, said patent being incorporated herein by reference.
As used herein, perfume includes fragrant substance: or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances. Such materials are often accompanied try auxiliary materials, such as fxatives, extenders, stabilizers and solvents. These auxiliaries are also included within the meaning of "perfume", as used herein. Typically, perfumes are complex mixtures of a plurality of organic compounds.
Examples of perfume ingredients useful in the perfumes of the present invention compositions include, but are not limited to, hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol; 2,6-dimethyl-2-actanol; 2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl-frans-2,6-octadien-1~-ol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2-methyl-3-(para-tert-butylphenyl}-propionaidehyde;
4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydraxyphenyi}-butan-2-one; 1-(2,6,6-trimethyl-2-c;yclohexen-1-yl}-2-buten-1-one; para-methoxyacetophenone; para-methoxy-alpha-phenylpropene; methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.
Additional examples of fragrance materials include, but are not limited to, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma;
methyl-2-(2-pentyl-3-oxo-cyclopentyi) acetate; beta-naphthol methylether;
methyl-beta-naphthylketone; coumarin; decyialdehyde; benzaldehyde; 4-tert-butylcyclohexyi acetate; alpha,alpha-dimethylphenethyl acetate;
methylphenylcarbinyl acetate; Schiffs base of 4-(4-hydroxy-4-methylpentyl}-3-cyclohexene-1-carboxaldehyde and methyl anthranulate; cyclic ethylenegiycol diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrite; ionone gamma methyl; ionone alpha; ionone beta; petitgrain; methyl cedrylone; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; ionone methyl;
methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ke~tone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;
Detailed description of the invention I-Product of reaction between an amino functional polymer and a perfume component An essential component of the invention is a product of reaction an amino functional polymer comprising at least one primary andlor secondary amine group and a perfume component, so called hereinafter "amine reaction product".
A- Amino functional polymer The amino functional polymer is characterized by an Odour Intensity Index of less than that of a 1 % solution of methylanthranilate in dipropylene glycol.
Odour Intensity Index method By Odour intensity Index, it meant that the pure chemicals were diluted at 1 %
in Dipropylene Glycol, odor-free solvent used in perfumery. This percentage is more representative of usage levels. Smelling strips, or so called "blotters", were dipped and presented to the expert panellist for evaluation. Expert panellists are assessors trained for at least six months in odor grading and whose gradings are checked for accuracy and reproducibility versus a reference on an on-going basis. For each an amino functional polymer, the panellist was presented two blotters: one reference (Me Anthranilate, unknown from the panellist) and the sample. The panellist was asked to rank both smelling strips on the 0-5 odor intensity scale, 0 being no odor detected, 5 being very strong odor present.
Results:
The following represents Odour Intensity Index of an amino functional poiymer suitable for use in the present invention and according to the above procedure.
In each case, numbers are arithmetic averages among 5 expert panellists and the results are statistically significantly different at 95% confidence level:
Methylanthraniiate 1 % (reference) 3.4 1,4-bis-(3-aminopropyl) piperazine (BNPP) 1% 1.0 A general structure for the amino functional polymer containing at least one primary amine group of the present invention, is as follows:
(NH2)n - [B]
wherein n is an index of at least 1 and B is the ~>olymer backbone. B can optionally comprise a branching group, C and hence the amino functional polymer is of the following formula:
(NH2)n - [B] - (C]x wherein x >_:0.
Amino functional polymer containing a secondary amine group have a structure similar to the above excepted that the polymer comprises one or more -NH-groups instead of -NH2. Further, the polymer structure may also have one or more of both -NH2 and -NH- groups.
The amino functional polymer of the present invention contains at least one free, unmodified primary andlor secondary amino group attached to the main chain by hydrogen substitution, or by other suitable insertion or substitution by groups referred to as R*. Also suitable is the amino functional polymer comprising an unmodified primary and/or secondary amino group present on side chain(s).
Preferably, the amino functional polymers of the presE:nt invention will comprise several amino groups, more preferably more than 10 amino groups. The amino functional polymers of the present invention will preferably present a molecular weight (M1I1~ ranging from 150 to 2.10EG; more preferably from 400-50,000;
most preferably from 600 to 40,000.
The amino functional polymer can be a linear homo-, co-polymer and optionally branched, grafted andlor cross-linked.
Suitable polymer backbone B for the purpose of the present invention have the following polymer units i (1 ) (2) F (3) -(CH2-CH)x- -( C- H )x- -(CH _ CHZ-O )x -F I
COOHCOOH
wherein x = 2-105 O
I
F=H, - NH2, - COOH, COOK*, -C - CH3, - O-C -CH3,- OH, - CN, - OR*, O
R*
\/ , \/ OH ~~~ ° N-~"O , O \ / N
I
Suitable branching units C for the polymer backbone B are 2,3 or 2,4 or 3,4 substitution _ _ i N ~ C N\
The polymer backbone B can also comprise insertion groups I such as i WO 00102982 PCTlUS99/15678 -O- ~ -O-O- . -O-, -O-~-O- . -RH- -(CH2~
x>_1 R* or H
-C- , -C-N- , -N- ~ 'C-N- . \C =C\
bH O R* or H R or H * ~ or H ' * R or H
R* or H -~-O- ~ O O
-N- ~ " ~ -O-S-O- , -S-Nt-1- ' -S
O O O O
O
\ / ~ O C \ j , O
The arrow indicates substitution in position 2.3 or 4 n -O_C \-/ C~O- -C \ / C- , ~ a -O O O O
The backbone (B) can also contain several insertion groups linked together:
e.g.
\ / \ / . -yCH,)~ C- . -(CH~)WN- \ /
O
wherein x>- 1.
The aminofunctional polymers of the present invention can further comprise substituents R* in the main chain or in the side chain(s). Typically, R*
replaces an hydrogen atom. This R* group can either be linked directly or via a linker group L to the main or side chain. Suitable linker groups L are the above mentioned insertion groups I.
R* groups are C1 to C22 alkyl, alkenyl, alkylbenzene chain andlor their corresponding substituted derivatives. Such corresponding substituted derivatives include alicyclic, aromatic, heteroaromatic or heterocyciic systems, either inserted in the main chain or incorporated by a substitution of an H
atom in the main chain; an insertion group E in the main chain, as defined herein above and/or an end group E as defined below.
Further, the polymer backbone B and R* encompass end groups E. Typically end groups E can be an H, NH2 groups, an aromatic, alicyclic, heteroaromatic or heterocyclic group including mono-, di-, oligo-, poly-sa~ccharides R* ~ CH
-OH, -OR*.. -NH,. -~( , -C-N-R* or H ~ -N -~ O ' R* or H I
R* or H CH
-S03H, -OS03H, -COOH.-COOK*.
_ I
\ / ~ ~ O ' ~ ~ H
CH3 CH,-CH,-OH
~N=CH3 ' X_~yCH3 ~ X=~N-CH,-CH_.,-OH . -C-OCH,-CH,-N+(CH3)3 CH3 X CH,-CH.,-OH CH3 -wherein Y-= is an anion like C1-,Br ,SO;~''' En addition, the R* group can also be modified via substitution of one or more H
atoms. Said substitution can either be an end group E: or an insertion group I
as defined above, where the insertion group is terminated by a H, E or R* group .
Preferred examples of suitable amino-functional polymers for use in the present invention are selected from the polyvinylamines, derivatives thereof, copolymer thereof, aikylene polyamine, polyaminoacid and copolymer thereof, cross-linked poiyaminoacids, amino substituted polyvinylalcohof, polyoxyethylene bis amine or bis. aminoalkyl, aminoalkyl piperazine and derivatives, N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA), and mixtures thereof.
Polyamino acid is one suitable and preferred class of amino-functional polymer.
Polyaminoacids are compounds which are made up of amino acids or chemicaily modified amino acids. They can contain alanine, serine, aspartic acid, arginine, valine, threonine, glutamic acid, leucine, cysteine, histidine, lysine, isoleucine, tyrosine, asparagine, methionine, proiine, tryptophan, phenylalanine, glutamine, glycine or mixtures thereof. In chemically modified amino acids, the amine or acidic function of the amino acid has reacted with a chemical reagent. This is often done to protect these chemical amine and acid functions of the amino acid in a subsequent reaction or to give special properties to the amino acids, like improved solubility. Examples of such chemical modifications are benzyloxycarbonyl, aminobutyric acid, butyl ester, pyroglutamic acid. More examples of common modifications of amino acids and small amino acid fragments can be found in the Bachem, 1996, Peptides and Biochemicals Catalog.
Preferred polyamino acids are polylysines, polyarginine, polygiutamine, poiyasparagine, polyhistidine, polytryptophane ar mixtures thereof. Most preferred are polylysines or poiyamino acids where more than 50% of the amino acids are lysine, since the primary amine function in the side chain of the lysine is the most reactive amine of all amino acids.
The preferred polyamino acid has a molecular weight of 500 to 10.000.000, more preferably between 5,000 and 750.000.
The polyamino acid can be cross linked. The cross linking can be obtained for example by condensation of the amine group in the side chain of the amino acid like lysine with the carboxyl function on the amino acid or with protein cross linkers like PEG derivatives. The cross linked polyamino acids still need to have free primary andlor secondary amino groups left for reaction with the active ingredient.
The preferred cross linked poiyamino acid has a molecular weight of 20.000 to 10.000.000, more preferably between 200.000 and 2.000.000.
The polyamino acid or the amino acid can be co-polymerized with other reagents like for instance with acids, amides, acyl chlorides. More specifically with aminocaproic acid, adipic acid, ethylhexanoic acid, caproiactam or mixture thereof. The molar ratio used in these copolymers ranges from 1:1 (reagent/
amino acid (lysine)) to 1:20, more preferably from 1:1 to 1:10.
The polyamino acid like pofylysine can be partially ethoxylated.
Examples and supply of polyaminoacids containing lysine, arginine, giutamime, asparagine are given in the Bachem 1996, Peptides and Biochemicals catalog.
The polyaminoacid can be obtained before reaction with the active ingredient, under a salt form. For example polylysine can be supplied as polylysine hydrobromide. Polylysine hydrobromide is commercially available from Sigma, Applichem, Bachem and Fluka.
Examples of suitable amino functional polymers containing at least one primary andlor secondary amine group for the purpose of the present invention are - Polyvinylamine with a MW of about 300-2.10Efi;
- Polyvinyiamine aikoxylated with a MW of about 600, 1200 or 3000 and an ethoxylation degree of 0.5;
- Polyvinylamine vinyialcohol - molar ratio 2:1, pofyvinylaminevinyiformarnide -molar ratio 1:2 and polyvinylamine vinyiformamide-molar ratio 2:1;
- Triethylenetetramine, diethylenetriamine, tetraethylenepentamine;
- Bis-aminopropylpiperazine;
Polyamino acid (L-lysine l lauric acid in a molar ratio of 10/1 ), Poiyamino acid (L-lysine I aminocaproic acid l adipic acid in a molar ratio of 5/511 ), ), Poiyamino acid (L-lysine / aminocaproic acid /ethylhexanoic acid in a molar ratio of 5/3/1 ) Poiyamino acid (polylysine-cocaprolactam); Polylys~ine hydrobromide, cross-linked polylysine, - amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
- polyoxyethylene bis [amine] available from e.g. Sigma;
- polyoxyethyiene bis [6-aminohexyl] available from e.g. Sigma;
- N,N'-bis-(3-aminopropyi)-1,3-propanediamine linear or branched (TPTA); and - 1,4-bis-(3-aminopropyl) piperazine {BNPP).
Preferred amino functional polymers containing at least one primary and/or secondary amine group are - polyvinylamines with a MW ranging from 600, 1200, 3K, 20K, 2bK or 50K;
- amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
polyoxyethylene bis [amine] available from e.g. Sigma;
- polyoxyethylene bis [fi-aminohexyl] available from e..g. Sigma;
- N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA);
- 1,4-bis-(3-aminopropyl) piperazine (BNPP);
- Polylysine hydrobromide;
cross-linked polylysine.
Furthermore, such amino functional polymers comprising at least one primary and/or secondary amine group and the amine reaction product provide fabric appearance benefits, in particular color care and protection against fabric wear.
Indeed, the appearance of fabrics, e.g., clothing, bedding, household fabrics like table linens is one of the area of concern to consumers. Indeed, upon typical consumer's uses of the fabrics such as wearing, washing, rinsing andlor tumble-drying of fabrics, a loss in the fabric appearance; which can be at least partly due to loss of color fidelity and color definition, is observed. Such a problem of color loss is even more acute after multiwash cycles. It has been found that the compositions of the present invention provide improved fabric appearance and protection against fabric wear and improved color care to laundered fabrics, especially after muitiwash cycles.
Therefore, the compositions of the present invention can provide simultaneously fabric care and long lasting perfume benefits.
B-Perfume Preferably, for the above mentioned compounds, by perfume ketone or aldehyde, it is meant any chain containing at least 1 carbon atom, preferably at least 5 carbon atoms.
A typical disclosure of suitable ketone and/or aldehydes, traditionally used in perfumery, can be found in "perfume and Flavor Chemicals", Vol. I and II, S.
Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5.
Perfume ketones components include components having odoriferous properties.
Preferably, for the above mentioned compounds, the perfume ketone is selected for its odor character from buccoxime; iso jasmone; methyl beta naphthyl ketone; musk indanone; tonaiid/musk plus; Alpha-Damascone, Beta-Damascone, Delta-Damascone, Iso-Damascone, Damascenone, Damarose, Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone, Alpha-lonone, Beta-lonone, Gamma-Methyl so-callecl lonone, Fleuramone, Dihydrojasrnone. Cis-Jasmone, lso-E-Super, Methyl- Cedrenyl-ketone or Methyl-Cedrylone, Acetophenone, Methyl-AcetophE:none, Para-Methoxy-Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-Acetone, Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery Ketone~ or Livescone, 6-Isopropyidecahydro-2-naphtone, Dimethyl-Octenon~:, Freskomenthe, 4-(1-Ethoxyvinyl)-3,3,5,5,-tetramethy(-Cyclohexanone, Methyl-Heptenone, 2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)-cyclopentanone, 1-(p-Menthen-6(2}-yl)-1-propanone, 4-(4-Hydroxy-3-methoxyphenyl)-2-butanone, 2-Acetyl-3,3-Dimethyl-Norbornane, 6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-C)amascol, Dulcinyl or Cassione, Gelsone, Hexalon, lsocyciemone E, Methyl Cyclocitrone, Methyl-Lavender-Ketone, Orivon, Para-tertiary-Butyl-Cyclohexanone, Verdone, Delphone, Muscone, Neobutenone, Plicatone, Veloutone, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Tetrameran, Undecaiactone and Gamma undecalactone.
For the above mentioned compounds, the more preferred ketones are selected for its odor character from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-ionone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof.
Perfume aldehyde components include components having odoriferous properties.
Preferably, for the above mentioned compounds, the perfume aidehyde is selected for its odor character from adoxal; anisic aidE:hyde; cymai; ethyl vanillin;
florhydral; helionai: heliotropin; hydroxycitronellai; koavone; lauric aldehyde;
lyral; methyl nonyl acetaldehyde; P. T, bucinal; phenyl acetaldehyde;
undecylenic aidehyde; vanillin; 2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amyl cinnamic aldehyde, 4-methoxybenzaidehyde, benzaldehyde, 3-(4-tert butylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyf propanal, 2-methyl-4-(2,6,6-trimethyl-2(1)-cyciohexen-1-yl) butanal, 3-phenyl-2-propenal, cis-/traps-3,7-dimethyi-2,6-octadien-1-al, 3,7-dimethyi-6-octen-1-al, [(3,7-dimethyl-6-octenyl)oxy] acetaldehyde, 4-isopropylbenzyaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyciohexen-1-carboxaidehyde, 2-methyl-3-(isopropyiphenyl)propanai, 1-decanal; decyl aldehyde, 2,6-dimethyi-5-heptenal, 4-(tricycto[5.2.1.0(2,6)]-decyiidene-8)-butanal, octahydro-4,7-methano-1 H-indenecarboxaldehyde, 3-ethoxy-4-hydroxy benzaldehyde, para-ethyl-alpha, alpha-dimethyi hydrocinnamaldehyde, alpha-methyl-3,4-(methyienedioxy)-hydrocinnamaidehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde, m-cymene-7-carboxaidehyde, alpha-methyl phenyl acetaldehyde, 7-hydroxy-3,7-dimethyl octanai, Undecenal, 2,4,6-trimethyl-3-cyciohexene-'I-carboxaldehyde, 4-{3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaidehyde, 1-dodecanal, 2,4-dimethyl cyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methyl pentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al, 2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal, dihydrocinnamic aldehyde, 1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5 or Ei methoxy0hexahydro-4,7-methanoindan-1 or 2- carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al, 4-hydroxy-3-methoxy benzaldehyde, 1-methyl-3-{4-methylpentyl)-3-cycihexenecarboxaldehyde, 7-hydroxy-3,7-dimethyl-octanal, traps-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde; 4-methylphenylacetaldehyde, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-cyclohexene carboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dime~thyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadien-1-al), hexahydro-4,7-methanoindan-1-carboxaldehyde, 2-methyl octanal, alpha-methyl-4.-(1-methyl ethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinene-2-propionaldehyde, para methyl phenoxy acetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethyl hexanal, Hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicycio[2.2.1]-hept-5-ene-2-carbaldehyde, 9-decenal, 3-nnethyl-5-phenyl-1-pentanal, rnethylnonyl acetaldehyde, hexanal, traps-2-hexenal, 1-p-menthene-q-carboxaldehyde and mixtures thereof.
More preferred aldehydes are selected for its odor character from 1-decanat, benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-1-carbaxaldehyde;
cis/traps-3,7-dimethyl-2,6-octadien-1-al; heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, alpha-n-hexyi cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal, traps-2-hexenal, and mixture thereof.
In the above list of perfume ingredients, sorne~ are commercial names conventionally known to one skilled in the art, and also includes isomers.
Such isomers are also suitable for use in the present invention.
In another embodiment, especially suitable for the purpose of the present invention are the perfume compounds, preferably the perfume ketoses or aldehydes, characterized by having a low Odor Detection Threshold. Such Odor Detection Threshold (ODT) should be lower than 1 ppm, preferably lower than 10ppb - measured at controlled Gas Chromatography {GC) conditions such as described here below. This parameter refers to the value commonly used in the perfumery arts and which is the lowest concentration at which significant detection takes place that some odorous material is present.
Please refer for example in "Compilation of Odor and Tasi:e Threshold Value Data (ASTM DS 48 A)", edited by F. A. Fazzalari, International Business Machines, Hopwell Junction, NY and in Catkin et al., Perfumery, Practice and Principles, John Willey & Sons, Inc., page 243 et seq (1994). For the purpose of the present invention, the Odor Detection Threshold is measured according to the following method The gas chromatograph is characterized to determine the exact volume of material injected by the syringe, the precise spfit ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain-length distribution. The air flow rate is accurately measured and, assuming the duration of a human inhalation to last 0.02 minutes, the sampled volume is calculated. Since the precise concentration at the detector at any paint in time is known, the mass per volume inhaled is known and hence the concentration of material. To determine the ODT of a perfume material, solutions are delivered to the sniff port at the back-calculated concentration. A panelist sniffs the GC effluent and identifies the retention time when odor is noticed.
The average over all panelists determines the threshold of noticeability. The necessary amount of analyte is injected onto the column to achieve a certain concentration, such as 10 ppb, at the detector. Typical gas chromatograph parameters for determining odor detection thresholds are listed below.
GC: 5890 Series Il with FID detector 7673 Autosampler Column: J&W Scientific DB-1 Length 30 meters ID 0.25 mm film thickness 1 micron Method:
Split Injection: 17/1 split ratio Autosampler: 1.13 microliters per injection Column Flow: 1.10 mUminute Air Flow: 345 mUminute Inlet Temp. 245°C
Detector Temp. 285°C
Temperature Information Initial Temperature: 50°C
Rate: 5C/minute Final Temperature: 280°C
Final Time: 6 minutes Leading assumptions: 0.02 minutes per sniff GC air adds to sample dilution Examples of such preferred perfume components are those selected from : 2-methyl-2-(para-iso-propyiphenyl)-propionaldehyde, 1-(2,6,6-trimethyl-2-cyclohexan-1-yl)-2-buten-1-one andlor para-methoxy-acetophenone. Even more preferred are the following compounds having an ODT <_ l0ppb measured with the method described above : undecylenic aldehydE~, undecalactone gamma, heliotropin, dodecalactone gamma, p-anisic aldehyde, pats hydroxy-phenyl-butanone, cymal, benzyl acetone, ionone alpha, p.t.bucinai, damascenone, ionone beta and methyl-nonyl ketone.
Typically the level of perfume is of from 10 to 90%, preferably from 30 to 85%, more preferably from 45 to 80% by weight of the amine reaction product.
Preferred amine reaction products are those resulting from the reaction of polyaminoacid like Polylysine, BNPP, or TPTA with one or more of the following Alpha Damascone, Delta Damascone, Canrone, fiedione, Florhydral, Lilial, Heliotropine, Gamma-Methyl-lonone and 2,~4-dimethyl-3-cyclohexen-1-carboxaldehyde, and mixture thereof.
Most preferred amine reaction products are those from the reaction of BNPP or TPTA with Alpha and Delta Damascone.
Process Preparation of the component is made as follows in the Synthesis Examples. In general, the nitrogen analogs of ketones and aldehyd~es are called azornethines, Schiff bases or the more preferred name imines. These imines can easily be prepared by condensation of primary amines and carbonyl compounds by elimination of water.
A typical reaction profile is as follows:
R,yR ' HEN.-R" ~- R--C-NH-R"
I
R' R
v /c=N-R" + HBO
R' a,~i-Unsaturated ketones do not only condense with amines to form imines, but can also undergo a competitive 1,4-addition to form ~3-;aminoketones.
WO 00!02982 PCT/US99/15678 R"
O
R-CH=CH-IC-R' + H N-R" ---~ f H O
R-CH-CH-C-R' By means of this simple method, compound and composition containing said compounds are made which achieve a delayed release of the active ingredient.
As can be observed, the perfume ingredient preferably needs to be present in equimolar amount to the amine function so as to enable the reaction to take place and provide the resulting amine reaction product. Of course, higher amount are not excluded and even preferred when the amine compound comprises more than one amine function.
Mechanism of release By the present invention, a delayed release of a perfume ingredient, i.e.
ketone or aldehyde is obtained. Not to be bound by theory, the release is believed to occur by the following mechanisms:
For imine compounds, the perfume components are released upon breaking down of the imine bond, leading to the release of the perfume component and of the primary amine compound. This can be achieved by either hydrolysis, photochemical cleavage, oxidative cleavage, or enzymatic cleavage.
For ~-aminoketone compounds, treatment with air moisture andlor water successfully releases the perfume component and the amine compound.
However, other means of release are not excluded like hydrolysis, photochemical cleavage, oxidative cleavage, or enzymatic cleavage.
Still other means of release for imine as well as ~-aminoketone compounds can be considered such as by the steaming step of ironing the treated fabric, tumble-drying, and/or wearing.
Laundry and cleaning compositions The present invention include both laundry and cleaning compositions which are typically used for Laundering fabrics and cleanings hard surfaces such as dishware, floors, bathrooms, toilet, kitchen and other surfaces in need of a delayed release of perfume ketone andlor aldehyde. Accordingly, by laundry and cleaning compositions, these are to be understood to include not only detergent compositions which provide fabric cleaning benefits, but also compositions such as hard surface cleaning which provide hard surface cleaning benefit.
Preferred are those laundry compositions which result in contacting the compound of the invention with fabric.
Preferably, the amine reaction products) which is incorporated into such laundry and cleaning compositions provides a dry surface Odour Index of more than 5 preferably at least '! 0.
By Dry Surface Odour Index, it is meant that the amine reaction products) provides a Delta of more than 5, wherein Delta is the difference between the Odour Index of the dry surface treated with amine reaction products) and the Odour Index of the dry surface treated with only the perfume raw material.
Measurement method of Dry Surface Odour Index:
For the above Dry Surface Odour Index, the amine reaction product suitable for use in the present invention needs to fulfill at least one of the following two tests.
Preferred amine reaction product suitable for use in the present invention fulfill both test.
1)-For fabric surface Product preparation:
The amine reaction product is added to the unperfumed product base.
The unperfumed product base, wherein the abreviations are as defined herein after for the examples, is as follows:
Composition . % by weight ~.AS 1 s NaSKS-6 TAED 2.4 Carbonate 1 Sodium Carbonate 1 HEDP 0.4 SRP1 0.2 Photobleach 0.013 Citric acid 1.0 Protease 0.3 Lipase 0.1 Cellulase 0.1 Amylase 0.3 Zeolilte 3.0 TFAA 3.0 QAS1 2.5 Silicone antifoam 1.0 Misclminors to balance to 100%
Levels of amine reaction product are selected so as to obtain an odour grade on the dry fabric of at least 20. After careful mixing, by shaking the container in case of a liquid, with a spatula in case of a powder, tlhe product is allowed to sit for 24 hrs.
Washing process:
The resulting product is added into the washing machine in the dosage and in the dispenser appropriate for its category. The quantity corresponds to recommended dosages made for the corresponding market products: typically between 70 and 150 g for a detergent powder or liquid via current dosing device like granulette, or ariellette. The load is composed of four bath towels (170g) using a Mieie W830 washing machine at 40°C short cycle, water input :15°Hardness at a temperature of 10-18°C, and full spin of 1200rpm.
The same process is applied for the corresponding free perfume ingredient in consideration and is used as the reference. Dosages, fabric toads and washing cycles for the reference and the sample are identical.
Drying Process:
Within two hours after the end of the washing cycle, the spinned but still wet fabrics are assessed for their odors using the scale mentioned below.
Afterwards, half of the fabric pieces are hung on a line for 24 hr drying, away from any possible contaminations. Unless specified, this drying takes place indoor. Ambient conditions are at temperature between 18-25C and air moisture between 50-80%. The other half is placed in a tumble drier and undergoes a full "very dry" cycle, i.e. in a Miele, Novotronic T430 set on program white-extra dry (full cycle). Tumble dry fabrics are also assessed on the next day. Fabrics are then stored in opened aluminum bags in an odor free room, and assessed again after 7 days.
Odor Evaluations:
Odor is assessed by expert panellist smelling the fabrics. A 0-100 scale is used for all fabric odor gradings. The grading scale is as follows 100 = extremely strong perfume odor 7a = very strong perfume odor 50 = strong odor 40 = moderate perfume odor = slight perfume odor 20 = weak perfume odor 10 = very weak perfume odor 0 = no odor A difference of more than 5 grades after one day and/or 7 days between the amine reaction product and the perfume raw material is statistically significant. A
difference of 10 grades or more after one day and/or 7 days represents a step-change. In other words, when a difference of grade of more than 5, preferably at least 10 is observed between the amine reaction product and the perfume raw material, after either 1 day or 7 days or both 1 day and 7 days, it can be concluded that the amine reaction product is suitable for use in the present invention, provided that the amine compound fulfill the Odour Intensity Index.
2)-For hard surface:
Product preparation:
The perfume raw material or blend thereof is added and carefully mixed at 0.255% in the unperfumed Hard Surface Cleaner base.
The unperfumed product base, wherein the abreviations ace as defined herein after for the examples, is as follows:
Composition for hard surface test % by weight C12-14 EO 5 2,~
C9-11 EO 5 2.5 ~S 0.8 Na2C03 0,2 Citric acid p.g Caustic acid 0.5 Fatty acid 0,5 SCS 1.5 Water &Misc/Minors to balance to 100%
After mixing and standing for 24 hrs, the homogeneity of the product is checked.
In case of phase separation due to poor solubility of the perfume ingredients) an appropriate amount of Sodium p. Cymene Sulfonate or another solubilising agent is added till a homogeneous solution is obtained.
Cleaning process:
Five grams of this solution are evenly applied on the upper side of a ceramic tile (875 square cm, e.g. from Vileroy-Boch). After 1 minute the tile is rinsed with 1 liter of tap water. The tile is then placed in a vertical position for 3 minutes to allow the rinse water to drip off.
Finally, the tile is placed in a clean and aerated perspex box {38 x 40 x 32 cm) with a removable cover that has a sliding-lid (10 x 10 cm) to allow expert evaluators to smell the interior phase of the box.
The odor in the box is evaluated just after placing the tile in it (fresh reading) and after 1, 2 and 6 hours.
Odor Evaluation:
The grading scale is as follows 50 = very strong odor 40 = strong odor 30 = moderate odor 20 = slight odor = weak odor 0 = no odor Every test includes a blanc (unperfumed Hard Surface Cleaner) and in the case of testing perfume precursor, so-called amine. reaction product the corresponding free perfume ingredient is also included so that the effect of the carrier is adequately measured.
Again as for the Dry surface Odour Index method for fabrics, a difference of more than 5 grades after 1 day andlor 7 days between , the amine reaction product and the perfume raw material is statistically significant. A
difference of 10 grades or more after 1 day andlor 7 days represents a step-change. In other words, when a difference of grade of more than 5, preferably at least 10 is observed between the amine reaction product and t:he perfume raw material, after either 1 day or 7 day or both 1 day and 7 days, it can be concluded that the amine reaction product is suitable for use in the present, provided that the amine compound fulfill the Odour Intensity Index.
The amine reaction product as defined herein before is typically comprised from 0.0001 % to 10%, preferably from 0.001% to 5%, and more preferably from 0.01 % to 2%, by weight of the composition. Mixture, of the compounds may also be used herein.
Incorporation of the amine reaction product in the laundry and cleaning compositions can conveniently be carried out, if necessary, by conventional incorporation means, such as by spray-on, encapsulation like starch encapsulation, e.g. as described in GB1464616, dry addition, or by encapsulation in cyclodextrin. Preferably, the amine reaction product is preformed before incorporation into the laundry and cleaning compositions. In other words, the perfume component and the amino functional polymer of the present invention are first reacted together to obtain tlhe resulting amine reaction product as defined in the present invention and only once formed incorporated into the laundry and cleaning compositions. By be;ing preformed before the incorporation in fully formulated composition, a better control of the compound being made is obtained. Hence, the interaction with perfume composition which may be present in fully formulated composition is avoided as well as side reaction that could occur. Further, by such means of incorporation, efficient control of the yield and purity of the compound is obtained.
Most preferably, when the laundry and cleaning composition comprises a perfume, the amine reaction product is incorporated in the composition separately from the perfume. By this means, the amine reaction product and its subsequent perfume release is more controlled.
Typically the laundry and cleaning composition comprises a detersive ingredient and further optional ingredients as described hereinafter as optional ingredients.
Detersive ingredients Non-limiting examples of surfactants useful herein typically at levels from 1 % to 55%, by weight, include the conventional C11-C1EI alkyl benzene sulfonates ("LAS"} and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the C10-C1g secondary (2,3) alkyl suff,ates of the formula CH3(CH2)x(CHOS03-M+) CH3 and CH3(CH2)y(CHOS03-M+) CH2CH3 where x and (y + 1 ) are integers..of at least 7, preferably ai: least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oley!
sulfate, the C10-C1g alkyl alkoxy sulfates ("AEXS"; especially x up to 7 EO ethoxy sulfates), C10-C1g alkyl alkoxy carboxyiates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C1 g alkyl poiyglycosides and their corresponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12-C1g alkyl e~thoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C12 alkyl phenol alkoxylates {especially ethoxylates and mixed ethoxylpropoxy), C12-C18 betaines and sulfobetaines ("sultaines"), C10-C~;g amine oxides, cationic surfactants and the like, can also be included in the overall compositions.
The C10-C1g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C1g N-methyiglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C1p-C1g N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C1g glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. if high sudsing is desired, the branched-chain C10-C1g soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfaci:ants are listed in standard texts.
Fully formulated laundry and cleaning compositions preferably contain, in addition to the hereinbefore described components, one or more of the following ingredients.
Builders Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1 % builder, preferably from 1 % to 80%. Liquid formulations typically comprise from 5% to 50%, mare typically 5% to 30%, by weight, of detergent builder. Granular formulations typically comprise from 1 % to 80%, more typically from 5% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and aikanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly those having a Si02:Na20 ratio in the range 1.0:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. 4,664,839. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Si05 morphology form of layered silicate. It can be prepared by method such as those described in DE-A-3,417,649 and DE-A-3,74:?,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSix02x+1 ~yH20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2SiO~i (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaiine~ earth and alkali metal carbonates as disclosed in DE 2,321,001.
Aluminosilicate builders are useful in the present invention. Aluminosiiicate builders are of great importance in most currently marketed heavy duty granutar detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
Mz/n~(A102)z(Si02)yj~xH20 wherein z and y are integers usually of at least 6, the molar ratio of z to y is in the range from 1.O to 0, and x is an integer from 0 to 264, and M is a Group IA or IIA element. e.g., Na, K, Mg, Ca with valence n.
Useful aluminosilicate ion exchange materials are commercially available.
These aiuminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is ciisciosed in U.S.
3,985,669.
Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP
and Zeoiite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Na l 2~(A102)12(Si02) 121~xH20 wherein x is from 20 to 30, especially 27. This matssrial is known as Zeolite A.
Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to; a wide variety of poiycarboxylate compounds.
As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylatE~s. Polycarbaxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanoiammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S.
3,128,287, U.S. 3,635,830. See also "TMSITDS" builders of U.S. 4,663,071.
Suitable ether polycarboxylates also include cyclic compounds, particularly aiicyclic compounds, such as those described in U.S. 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypoiycarboxylates, copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid anti nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, pyromeliitic, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite andlor layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the preaent invention are the 3;3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
4,566,984. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in E=P 0,200,263.
Other suitable polycarboxylates are disclosed in U.S 4,144,226 and in U.S.
3,308,067. See also U.S. 3,723,322.
Fatty acids, e.g., C12-C1g monocarboxyfic acids such as oleic acid and/or its salts, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate andlor the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
In situations where phosphorus-based builders can 1be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripoiyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates {see, for example, U.S. Patents 3,159,581; 3,213,030;3,422,021; 3,400,148 and 3,422,137) can also be used.
WO 00!02982 PCT/US99/15678 Bleaching ComAOUnds - Bleaching Aqents and Bleach Activators The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing .a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from to 30%, more typically from 5% to 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator, The bleaching agents used herein can be any. of the bleaching agents useful for detergent compositions in textile cleaning or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents like hypochiorite bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein. When hypochiorite is used, a highly preferred hypochlorite bleaching component is an alkali metal hypochlorite. Although alkali metal hypochlorites are preferred, other hypochiorite compounds may also be used herein and can be selected from calcium and magnesium hypochlorite. A preferred alkali metal hypochlorite for use herein is sodium hypochlorite.
Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents <~nd salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S 4,483,781, U.S 740,446, EP 0,133,354, and U.S 4,412,934.
Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S 4,634,551.
Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1,000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1,250 micrometers.
Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Sofvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution {i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S 4,915,854, and U.S 4,412,934. The nonanoyloxybenzene sulfonate (NOBS), 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate (ISONOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L.
wherein R1 is an alkyl group containing from 6 to '12 carbon atoms, R2 is an alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is any suitable leaving group. A
leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesuifonate, (6-nonanamidacaproyl)oxybenzene sulfonate, (6-decanamido-caproyl)oxybenzenesuifonaite, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723. ,A highly preferred activator of the benzoxazin-type is:
O
II
CEO
~~C o.J
N
Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
s~0 C-CH2-CH2\ 6-O C-CHz-CH2 R C-N~CH2-CH2~CH2 R C-NCH - ~ H
wherein R6 is H or an alkyl, aryl, aikoxyaryl, or alkaryl group containing from 1 to 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimet:hylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolac~am, undecenoyi valerolactam, nonanoyi valeroiactam, 3,5,5-trimethylhexanoyi valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, is:>ued to Sanderson, October 8, 1985; incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agenta are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc andlor aluminum phthalocyanines. See U.S. 4,033,718. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well-known in the art and include, for example, the manganese-based catalysts disclosed in U.S. 5,246,621, U.S.
5,244,594; U.S. 5,194,416; U.S. 5,114,606; and E:P 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include MnlV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, Mnlll2 (u-O}1(u-\:
OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2_{C104)2, MnlV4(u-O)6(1,4,7-triazacyclononane)4(CI04)4, MnIIIMniV4(u-O)1(u-C)Ac)2_(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)-{OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and ll.S. 5,114,611. The use of manganese with various complex Iigands to enhances bleaching is also reported in the following US Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779;
5,280,117; 5,274,147; 5,153,161; and 5,227,084.
As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in thie aqueous washing liquor, and will preferably provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the laundr)r liquor.
Briqhteners The compositions herein can also optionally contaiin from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compasi!tions herein will preferably comprise from 0.001 % to 1 % by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
Rt R
--N H H rl N ~~--N a C=C ~ N--~{~ N
j"-N H H rf --C
R~~ SO;M S03M R~
wherein R1 is selected from aniiino, N-2-bis-hydroxyethyi and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyi-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anifino, R2 is N-2-l:>is-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. Tinopa!-UNPA-GX
is the preferred hydrophilic optical brightener useful in the rinse added compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, they 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 SBM-GX~ by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a canon such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-yi)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX~ by Ciba Geigy Corporation.
Soil Release Agent In the present invention, an optional soil release agent can be added. Typical levels of incorporation in the composition are from 0°~o to 10%, preferably from 0.2% to 5%, of a soil release agent. Preferably, such a soil release agent is a polymer.
Soil Release agents are desirably used in fabric softening compositions of the instant invention. Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions of this invention.
Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophiiize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
If utilized, soil release agents will generally comprise from about 0.01 % to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1 % to about 5%. preferably from about 0.2% to about 3.0%.
The following, all included herein by reference, describe soil release polymers suitable for use in the present invention. U.S. 3,959.230 Hays, issued May 25, 1976; U.S. 3,893,929 Basadur, issued Juiy 8, 1975; U.S. 4,000,093, Nicol, et al., issued December 28, 197fi; U.S. Patent 4.702,857 Gosselink, issued October 27, 1987; U.S. 4,968,451, Scheibel et al., issued November 6; U.S.
4,702,857, Gosselink, issued October 27, 1987; U.S. 4,711,730, Gosselink et al., issued December 8, 1987; U.S. 4,721,580, Gosaelink, issued January 26, 1988; U.S. 4,877,896, Maidonado et al., issued October 31, 1989; U.S.
4,956,447, Gosselink et al., issued September 11, 1990; U.S. 5,415,807 Gosselink et al.; issued May 16. 1995; European Patent Application 0 219 048, published April 22, 1987 by Kud, ef al..
Further suitable soil release agents are described in I,~,S. 4,201,824, Vioiland et al.; U.S. 4,240,918 I_agasse et al.; U.S. 4,525,524 Tung et al.; U.S.
4,579,681, Ruppert et al.; U.S. 4,240,918; U.S. 4,787,989; U.S. 4,525,524; EP 279,134 A, 1988, to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE
2,335,044 to Uniiever N. V., 1974 all incorporated herein by reference.
Commercially available soil release agents include the METOLOSE SM100, METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN
type of material, e.g., SOKALAN HP-22, available from BASF (Germany}, ZELCON 512fi (from Dupont} and MILEASE T (from iCl).
Scum Dispersant In the present invention, the premix can be combined with an optional scum dispersant, other than the soil release agent, and heated to a temperature at or above the melting points) of the components.
The preferred scum dispersants herein are formE:d by highly ethoxylating hydrophobic materials. The hydrophobic material can be a fatty alcohol, fatty acid, fatty amine, fatty acid amide, amine oxidE~, quaternary ammonium compound, or the hydrophobic moieties used to form :SOiI release polymers. The preferred scum dispersants are highly ethoxylate:d, e.g., more than 17, preferably more than 25, more preferably more than 4~0, moles of ethylene oxide per molecule on the average, with the poiyethylene~ oxide portion being from 76% to 97%, preferably from 81 % to 94%, of the total molecular weight.
WO 00102982 PCTlUS99/15678 The level of scum dispersant is sufficient to keep the scum at an acceptable, preferably unnoticeable to the consumer, level under the conditions of use, but not enough to adversely affect softening. For some purposes it is desirable that the scum is nonexistent. Depending on the amount of anionic or nonionic detergent, etc., used in the wash cycle of a typical laundering process; the efficiency of the rinsing steps prior to the introduction of the compositions herein, and the water hardness, the amount of anionic or nonionic detergent surfactant and detergency builder (especially phosphates and zeolites) entrapped in the fabric (laundry) will vary. Normally, the minimum amount of scum dispersant should be used to avoid adversely affecting softening properties. Typically scum dispersion requires at least 2%, preferably at least 4% (at least 6% and preferably at least 10% for maximum scum avoidance) based upon the level of softener active. However, at levels of 10% (relative to the softener material) or more, one risks loss of softening efficacy of the product especially when the fabrics contain high proportions of nonionic surfactanf: which has been absorbed during the washing operation.
Preferred scum dispersants are: Brij 700~; Varonic U-250~; Genapol T-500~, Genapol T-800~; Plurafac A-79~; and Neodol 25-50U.
Bactericides Examples of bactericides used in the composition~~ of this invention include glutaraldehyde, formaldehyde, 2-bromo-2-nitro-propane-1,3-dioi sold by inolex Chemicals, located in Philadelphia, Pennsylvania,. under the trade name Bronopol~, and a mixture of 5-chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-isothiazoiine-3-one sold by Rohm and Haas Company under the trade name Kathon 1 to 1,000 ppm by weight of the agent.
Perfume The present invention can contain any detergent compatible perfume. Suitable perfumes are disclosed in U.S. Pat. 5,500,138, said patent being incorporated herein by reference.
As used herein, perfume includes fragrant substance: or mixture of substances including natural (i.e., obtained by extraction of flowers, herbs, leaves, roots, barks, wood, blossoms or plants), artificial (i.e., a mixture of different nature oils or oil constituents) and synthetic (i.e., synthetically produced) odoriferous substances. Such materials are often accompanied try auxiliary materials, such as fxatives, extenders, stabilizers and solvents. These auxiliaries are also included within the meaning of "perfume", as used herein. Typically, perfumes are complex mixtures of a plurality of organic compounds.
Examples of perfume ingredients useful in the perfumes of the present invention compositions include, but are not limited to, hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol; 2,6-dimethyl-2-actanol; 2,6-dimethyl-7-octen-2-ol; 3,7-dimethyl-3-octanol; 3,7-dimethyl-frans-2,6-octadien-1~-ol; 3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol; 2-methyl-3-(para-tert-butylphenyl}-propionaidehyde;
4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; ethyl-3-methyl-3-phenyl glycidate; 4-(para-hydraxyphenyi}-butan-2-one; 1-(2,6,6-trimethyl-2-c;yclohexen-1-yl}-2-buten-1-one; para-methoxyacetophenone; para-methoxy-alpha-phenylpropene; methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.
Additional examples of fragrance materials include, but are not limited to, orange oil; lemon oil; grapefruit oil; bergamot oil; clove oil; dodecalactone gamma;
methyl-2-(2-pentyl-3-oxo-cyclopentyi) acetate; beta-naphthol methylether;
methyl-beta-naphthylketone; coumarin; decyialdehyde; benzaldehyde; 4-tert-butylcyclohexyi acetate; alpha,alpha-dimethylphenethyl acetate;
methylphenylcarbinyl acetate; Schiffs base of 4-(4-hydroxy-4-methylpentyl}-3-cyclohexene-1-carboxaldehyde and methyl anthranulate; cyclic ethylenegiycol diester of tridecandioic acid; 3,7-dimethyl-2,6-octadiene-1-nitrite; ionone gamma methyl; ionone alpha; ionone beta; petitgrain; methyl cedrylone; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; ionone methyl;
methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ke~tone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; benzophenone;
acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetrarnethyl indane; 1-dodecanal; 7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl tricyclodec;an;
cyclopentadecanolide;
16-hydroxy-9-hexadecenoic acid lactose; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyicyclopenta-gamma-2-benzopyrane; ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1 b]furan; cedrol; 5-(2;2,3-trimethylcyclopent-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3~-cyciopenten-1-yl)-2-buten-1-0l; caryophyllene alcohol; cedryl acetate: para-tert-butylcyclohexyl acetate;
patchouli; olibanum resinoid; labdanum; vetivert; copaiba balsam; fir balsam;
and condensation products of: hydroxycitronellal and methyl anthranilate;
hydroxycitronellai and indol; phenyl acetaldehyde and indol; 4-(4-hydroxy-4-methy! pentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate.
More examples of perfume components are, geraniol; geranyl acetate; iinalool;
linalyl acetate; tetrahydrolinalool; citroneilol; citronellyl acetate;
dihydromyrcenol;
dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethyl acetate; bE~nzyl alcohol; benzyl acetate;
benzyi salicylate; benzyl benzoate; styrallyl acetate; dimethyibenzylcarbinol;
trichloromethylphenylcarbinyl methylpfienylcarbinyl acetate; isononyl acetate;
vetiveryi acetate; vetiverol; 2-methyl-3-(p-tert-butyl>henyl)-propanal; 2-methyl-3-(p-isopropyiphenyl)-propanal; 3-(p-tert-butylphenyl)-propanal; 4-(4-methyl-3-pentenyl)-3-cyciohexenecarbaldehyde; 4-acet:oxy-3-pentyltetrahydropyran;
methyl dihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyciopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehyde dimethylac~etal; phenyiacetaldehyde diethylacetal; geranonitriie; citroneilonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedryi methylether; isolongifolanone; aubepine nitrite;
aubepine; heliotropine; eugenol; vanillin; Biphenyl oxide; hydroxycitronellal ionones; methyl ionones; isomethyi ionomes; irone~s; cis-3-hexenol and esters thereof; indane musk fragrances; tetralin musk fragrances; isochroman musk fragrances; macrocyclic ketones; macroiactone musk fragrances; ethylene brassylate.
The perfumes useful in the present invention compositions are substantially free of halogenated materials and nitromusks.
Suitable solvents, diiuents or carriers for perfumes ingredients mentioned above are for examples, ethanol, isopropanol, diethylen~e glycol. monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc. The amount of such solvents, diluents or carriers incorporated in the perfumes is preferably kept to the minimum needed to provide a homogeneous perfume solution.
Perfume can be present at a level of from 0% to 10%, preferably from 0.1 % to 5%, and more preferably from 0.2% to 3%, by weight of the finished composition. Fabric softener compositions of the present invention provide improved fabric perfume deposition.
Chelatinc~Agents The compositions and processes herein can optionally employ one or more copper andlor nickel chelating agents ("chelators"). Such water-soluble chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. The whiteness andlor brightness of fabrics are substantially improved or restored by such chelating agents and the stability of the materials in the compositions are improved. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional cheiating agents include ethylenediaminetetracetates, N-hydroxyethyle~thylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra-aminehexacetates, diethyierietriaminepentaacetates., and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as. chelating agents in the compositions of-the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionaliy-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkin;~.
WO 00102982 PCTlUS99J15678 The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the dike.
Preferred chelating agents include DETMP, DETPA, NTA, EDDS and mixtures thereof.
If utilized, these chelating agents will generally comprise from about 0.1 %
to about 15% by weight of the fabric care compositions (herein. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to, about 3.0%
by weight of such compositions.
Crystal growth inhibitor component The compositions of the present invention can further contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01 % to 5%, more preferably from 0.1 % to 2% by weight of the compositions.
By organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sec#uestrant components.
The organo diphosphonic acid is preferably a C1-C~ diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
Still useful herein as crystal growth inhibitor are the organic monophosphonic acid Organo monophosphonic acid or one of its salts or compfexes is also suitable far use herein as a CGI.
By organo monophosphonic acid it is meant herein an organo monophosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrants.
The organo monophosphonic acid component may be present in its acid form or in the form of one of its salts or complexes with a suitable counter cation.
Preferably any salts/complexes are water soluble, with the alkali metal and alkaline earth metal salts/complexes being especially preferred.
A preferred organo monophosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid commercially available from Bayer under the tradename of Bayhibit.
Enzyme The compositions and processes herein can optionally employ one or more enzymes such as lipases, proteases, cellulase, amylases and peroxidases. A
preferred enzyme for use herein is a cellulase enzyme. Indeed, this type of enzyme will further provide a color care benefit to the; treated fabric.
Cellulases usable herein include both bacterial and fungal types, preferably having a pH
optimum between 5 and 9.5. U.S. 4,435,307 disctoses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and ceilulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~ aind CELLUZYMEC~ (Novo}
are especially useful. Other suitable cellulases are also disclosed in WO
91/17243 to Novo, WO 96/34092, WO 9fil34945 and EP-A-0,739,982. In practical terms for current commercial preparations, typical amounts are up to mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial enzyme preparation. In the particular cases where activity of the enzyme preparation can be defined otherwise such as with cellulases, corresponding activity units are preferred (e.g. CEVU or cellulase Equivalent Viscosity Units).
Far instance, the compositions of the present invention can contain cellulase enzymes at a level equivalent to an activity from 0.5 to 1000 CEVUlgram of composition. Cellulase enzyme preparations used for the purpose of formulating the compositions of this invention typically have an activity comprised between 1,000 and 10,000 CEVUlgram in liquid form, around 1,000 CEVUlgram in solid form.
Clay The compositions of the invention may preferably contain a clay, preferably present at a level of from 0.05% to 40%, more ~prefPrabiy from 0.5% to 30%;
most preferably from 2% to 20% by weight of the composition. For clarity, it is noted that the term clay mineral compound, as used herein, excludes sodium aiuminosilicate zeolite builder compounds, which hovuever, may be included in the compositions of the invention as optional components.
One preferred clay may be a bentonite clay. Highly preferred are smectite clays, as for example disclosed in the US Patents No.s 3,862,058 3,948,790, 3,954,632 and 4,062,647 and European Patents No.s EP-A-299,575 and EP-A-313,146 all in the name of the Procter and Gamble Company.
The term smectite clays herein includes both the clays in which aluminium oxide is present in a silicate lattice and the clays in which magnesium oxide is present in a silicate lattice. Typical smectite clay compounds include the compounds having the general formula AI2(Si205)2(OH)2.nH20 amd the compounds having the general formula Mg3(Si205)2(OH)2.nH20. Smectite clays tend to adopt an expandable three layer structure.
Specific examples of suitable smectite clays includes those selected from the classes of the montmorillonites, hectorites, vol~chonskoites, nontronites, saponites and sauconites, particularly those having an alkali or alkaline earth metal ion within the crystal lattice structure. Sodium or calcium montmorillonite are particularly preferred.
Suitable smectite clays, particularly montmoriilonitEa, are sold by various suppliers including English China Clays, Laviosa, Georgia Kaolin and Colin Stewart Minerals.
Clays for use herein preferably have a particle diimension of from l0nm to 800nm more preferably from 20nm to 500 mm, most preferably from 50nm to 200 mm.
Particles of the clay mineral compound may be included as components of agglomerate particles containing other detergent compounds. Where present as such components, the term "largest particle dimension" of the clay mineral compound refers to the largest dimension of the clay mineral component as such, and not to the agglomerated particle as a whole.
Substitution of small rations, such as protons, sodium ions, potassium ions, magnesium ions and calcium ions, and of certain organic molecules including those having positively charged functional groups can typically take place within the crystal lattice structure of the smectite clays. A clay may be chosen for its ability to preferentially absorb one ration type, such ability being assessed by measurements of relative ion exchange capacity. The smectite clays suitable herein typically have a ration exchange capacity of at least 50 meq/100g. U.S.
Patent No. 3,954,fi32 describes a method for measurement of ration exchange capacity.
The crystal lattice structure of the clay mineral compounds may have, in a preferred execution, a cationic fabric softening agent substituted therein.
Such substituted clays have been termed 'hydrophobic:ally activated' clays. The cationic fabric softening agents are typically present at a weight ratio, cationic fabric softening agent to clay, of from 1:200 to 7:11); preferably from 1:100 to 1:20. Suitable cationic fabric softening agents incfude> the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 27fi and EP-B-0 011 340.
A preferred commercially available "hydrophobicaily activated" clay is a bentonite clay containing approximately 40% by weight of a dimethyi ditallow quaternary ammonium salt sold under the tradenarr~e Claytone EM by English China Clays International.
In a highly preferred embodiment of the invention, the clay is present in an intimate mixture or in a particle with a humectant and a hydrophobic compound, preferably a wax or oil, such as paraffin oil. Preferred humectants are organic compounds, including propylene glycol, ethylene glycol; dimers or trimers of glycol, most preferably glycerol. The particle is preferably an agglomerate.
Alternatively, the particle may be such that the wax or oil and optionally the humeetant form an encapsulate on the clay or alternatively, the clay be a encapsulate for the wax or oil and the humectant. li: may be preferred that the particle comprises an organic salt or silica or silicate.
However, in another embodiment of the invention, the clay is preferably mixed with . one or more surfactants and optionally builders and optionally water, in which case the mixture is preferably subsequently dried: Preferably, such a mixture is further processed in a spray-drying method to obtain a spray dried particle comprising the clay.
It may be preferred that the flocculating agent is also comprised in the particle or granule comprising the clay.
It may also be preferred that the intimate mixture comprises a cheiating agent.
Flocculatingi agent The compositions of the invention may contain .a clay flocculating agent, preferably present at a level of from 0.005% to 10%, more preferably from 0.05% to 5%, most preferably from 0.1 % to 2% by weight of the composition.
The clay flocculating agent functions such as to bring together the particles of clay compound in the wash solution and hence to aid their deposition onto the surface of the fabrics in the wash. This functional requirement is hence different from that of clay dispersant compounds which are commonly added to laundry detergent compositions to aid the removal of clay soils from fabrics and enable their dispersion within the wash solution.
Preferred as clay flocculating agents herein are organic polymeric materials having an average weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000.
Suitable organic polymeric materials comprise homopolymers or copolymers containing monomeric units selected from aikylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Homopoiymers of, on particular, ethylene oxide, but also acrylamide and acrylic acid are preferred.
European Patents No.s EP-A-299,575 and EP-A-3'13,146 in the name of the Procter and Gamble Company describe preferred organic polymeric clay flocculating agents for use herein.
The weight ratio of clay to the flocculating polymer is preferably from 1000:1 to 1:1, more preferably from 500:1 to 1:1, most preferably from 300:1 to 1:1, or even more preferably from 80:1 to 10:1, or in certain applications even from 60:1 to 20:1.
Inorganic clay flocculating agents are also suitable therein, typical examples of which include lime and alum.
The flocculating agent is preferably present in a detergent base granule such as a detergent agglomerate, extrudate or spray-dried particle, comprising general3y one or more surfactants and builders.
Effervescent Effervescent means may also be optionally used in the compositions of the invention.
Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate, to produce carbon dioxide gas, i.e. C6H8O7 + 3NaHC03 ~ Na3CgH5O7 + 3C02 1' + 3H20 Further examples of acid and carbonate sources and other effervescent systems may be found in : (Pharmaceutical Dosage Forms : Tablets Volume 1 Page 287 to 291 ).
Carbonate salts Suitable alkali andl or earth alkali inorganic carbonate salts herein include carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like amongst which sodium and potassium ca:~bonate are preferred. Suitable bicarbonates to be used herein include any alkali metal salt of bicarbonate like lithium, sodium, potassium and the like, amongst which sodium and potassium bicarbonate are preferred. However, the choice of carbonate or bicarbonate or mixtures thereof may be made depending on the pH desired in the aqueous medium wherein the granules are dissolved. Far example where a relative high pH is desired in the aqueous medium (e.g., above pH 9.5) it may be preferred to use carbonate alone or to use a combination of carbonate and bicarbonate wherein the level of carbonate is higher than the level of bicarbonate. The inorganic alkali and/ or earth alkali carbonate salt of the compositions of the invention comprises preferably a potassium or more preferably a sodium salt of carbonate andl or bicarbonate. Preferably, the carbonate salt comprises sodium carbonate, optionally also a sodium bicarbonate.
The inorganic carbonate salts herein are preferably present at a level of at least 20% by weight of the composition. Preferably they are present at a level of at least 23% or even 25% or even 30% by weight, preferably up to about 60% by weight or more preferably up to 55% or even 50% by weight.
They may be added completely or partially as separate powdered or granular component, as co-granules with other detergent ingredients, for example other salts or surfactants. In solid detergent compositions of the invention, they may also completely or partially be present in detergent granules such as agglomerates or spray dried granules.
In one embodiment of the invention, an effervescence source is present, preferably comprising an organic acid, such as carboxylic acids or aminoacids, and a carbonate. Then it may be preferred that part or all of the carbonate salt herein is premixed with the organic acid, and thus present in an separate granular component.
Preferred effervescent source are selected from compressed particles of citric acid and carbonate optionally with a binder: and particle of carbonate, WO 00102982 PCT/US991156'78 bicarbonate and malic or malefic acid in weight ratios of 4:2:4. The dry add form of citric acid and carbonate are preferably used.
The carbonate may have any particle size. In one embodiment, in particular when the carbonate salt is present in a granule and not as separately added compound, the carbonate salt has preferably a volume median particle size from 5 to 375 microns, whereby preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume, has a particle size of from to 425 microns. More preferably, the carbon dioxide source has a volume median particle size of 10 to 250, whereby preferably at least 60 %, or even at feast 70% or even at least 80% or even at least 90% by volume, has a particle size of from 1 to 375 microns; or even preferably a volume median particle size from 10 to 200 microns, whereby preferably at least 60 %, preferably at least 70% or even at least 80% or even at least 90% by volume, has a particle size of from 1 to 250 microns.
In particular when the carbonate salt is added as separate component, so to say 'dry-added' or admixed to the other detergent ingredients, the carbonate may have any particle size, including the above specified particle sizes, but preferably at least an volume average particle size of 200 microns or even 250 microns or even 300 microns.
It may be preferred that the carbon dioxide source of the required particle size is obtained by grinding a larger particle size materiiai, optionally followed by selecting the material with the required particle size by any suitable method.
Whilst percarbonate salts may be present in the compositions of the invention as a bleaching agent, they are not included in the carbonate salts as defined herein Other preferred optional ingredients include enzymes stabilisers, polymeric soil release agents, rnateriais effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process (i.e., dye transfer inhibiting agents), polymeric dispersing agents, suds suppressers, optical brighteners or other brightening or whitening agents, anti-static agents, other active ingredients, carriers, hydrotropes: processing aids, dyes or pigments, solvents for liquid formulations and solid fillers for bar compositions.
Form of the composition The composition of the invention may take a variety of physical form including liquid, gel, foam in either aqueous or non-aqueous form, granular and tablet forms.
Liquid detergent compositions can contain water and other solvents as carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubiiizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
Granular detergents can be prepared, for example, by spray-drying (final product density 520 gll) or agglomerating (anal product density above 600 g/l) the Base Granule. The remaining dry ingredients can then be admixed in granular or powder form with the Base Granule, for example in a rotary mixing drum, and the liquid ingredients (e.g., nonionic surfactant and perfume) can be sprayed on.
The detergent compositions herein wilt preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis; acids, etc., and are well~known to those skilled in the art.
When in a liquid form, the composition may also be dispensed by a dispensing means such as a spray dispenser, or aerosol dispenser.
S~~ray Dispenser The present invention also relates to such compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabric articles andlor surfaces with said compasiiuons containing the amine reaction product and other ingredients (exannples are cyclodextrins, polysaccharides, polymers, surfactant, perfume, softener} at a level that is effective, yet is not discernible when dried on the surfaces. The spray dispenser comprises manually activated and non-manual powered (operated) spray means and a container containing the treating composition. Typical disclosure of such spray dispenser can be found in WO 96/04940 page 19 line 21 to page 22 line 27. The articles of manufacture preferably are in association with instructions for use to ensure that the consumer applies sufficient ingredient of the composition to provide the desired benefit. Typical compositions to be dispensed from a sprayer contain a level of amine reaction product of 'from about 0.01 % to about 5%, preferably from about 0.05% to about 2%, more preferably from about 0.1 to about 1 %, by weight of the usage composition.
Method of use The composition of the invention are suitable for use in any step of the domestic treatment, that is a pre-treatment composition, as a wash additive, as a composition suitable for use in the laundry and cleaning process. Obviously, multiple application can be made such as treating the fabric with a pre-treatment composition of the invention and thereafter with the composition suitable for use in the laundry process.
Also provided herein is a method for providing a delayed release of an active ketone or aldehyde which comprises the step of contacting the surface to be treated with a compound or composition of the invention, and thereafter contacting the treated surface with a material, preferably an aqueous medium like moisture or any other means susceptible of releasing the perfume from the amine reaction product.
By "surface", it is meant any surface onto which tree compound can deposit.
Typical examples of such material are fabrics, hard surfaces such as dishware, floors, bathrooms, toilet, kitchen and other surfaces in need of a delayed release of a perfume ketone and/or aldehyde such as that with litter like animal litter.
Preferably, the surface is selected from a fabric, a tile, a ceramic; more preferably is a fabric.
By "delayed release" is meant release of the active component (e.g perfume) over a longer period of time than by the use of the active (e.g., perFume) itself.
Abbreviations used in the followina laundr~r and cleanina composition Examples In the laundry and cleaning compositions, the abbreviated component identifications have the following meanings:
In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS : Sodium linear C11_13 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate CxyAS : Sodium C1x - C1y alkyl sulfate C46SAS : Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS : Sodium C1x-C1y alkyl sulfate condensed with z moles of ethylene oxide CxyEz : C1x-C1y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS : R2.N+{CH3)2(C2H40H) ~nrith R2 = C12 - C14 QAS 1 : R2.N+(CHg}2(C2H40H) with R2 = Cg - C11 APA : Cg - C10 amido propyl dimethyl amine Soap : Sodium linear alkyl carboxylate derived from an 80120 mixture of tallow and coconut tatty acids STS : Sodium toluene sulphonate CFAA : C12-C14 (coco} alkyl N-methyl glucamide TFAA : C16-C1g alkyl N-methyl g~iucamide TPKFA : C12-C14 toPPed whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate TSPP : Tetrasodium pyrophosphate Zeolite A : Hydrated sodium aluminosilicate of formula Nal2(A102Si02)12.27Ha0 having a primary particle size in the range from 0.1 to 10 micrometers {weight expressed on an anhydrous basis) NaSKS-6 : Crystalline layered silicatE: of formula 8-Na2Si205 Citric acid : Anhydrous citric acid Borate : Sodium borate Carbonate : Anydrous sodium carbonate with a particle size between 200pm and 9001am Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400ym and 1200Nm Silicate : Amorphous sodium silical;e (Si02:Na20 = 2.0:1) Sulfate : Anhydrous sodium sulfate:
Mg sulfate : Anhydrous magnesium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425pm and 850um MA/AA : Copolymer of 1:4 malleiclacrylic acid, average molecular weight about 70,000 MAIAA ~( 1 ) Copolymer of 4:6 malleic/acryiic acid, average :
molecular weight about 11),000 AA : Sodium polyacrylate polymer of average molecular weight 4,500 CMC : Sodium carboxymethyl cellulose Cellulose ether Methyl cellulose ether with a degree of :
polymerization of 650 available from Shin Etsu Chemicals Protease : Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries AIS under the tradename Savinase Protease I : Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.
Alcalase : Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase : Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120~T
Lipase : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipase {1) : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipotase Ultra Endolase : Endogtucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A!S
PB4 : Sodium perborate tetrahydrate of nominal formula NaB02.3H20.H202 PB1 : Anhydrous sodium perborate bleach of nominal fom~ula NaB02.H202 Percarbonate : Sodium percarbonate of nominal formula 2Na2C03.3H202 NOBS : Nonanoyioxybenzene suifonate in the form of the sodium salt NAC-OBS : {6-nonamidocaproyl) oxybenzene sulfonate TAED : Tetraacetylethylenediamine DTPA : Diethylene triamine pentaacetic acid DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename bequest 2060 EDDS : Ethytenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.
Photoactivated Sulfonated zinc phthlocyanine encapsulated : in bleach (1) dextrin soluble polymer Photoactivated Sulfonated alumino phthlocyanine encapsulated : in bleach (2) dextrin soluble polymer Brightener 1 Disodiurn 4,4'-bis(2-suiphostyryl)biphenyl :
Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-:
triazin-2-yl)amino) stilbene:-2:2'-disuifonate HEDP : 1,1-hydroxyethane diphos;phonic acid PEGx : Polyethylene glycol, with a molecular weight of x (typically 4,000) PEO : Polyethylene oxide, with an average molecular weight of 50,000 TEPAE : Tetraethyienepentaamine ethoxyiate PVI : Polyvinyl imidosole, witlh an average molecular weight of 20,000 WO 00/02982 PCTlUS99115678 PVP : Polyvinylpyrolidone polymer, with an average molecular weight of 60,00() PVNO . Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,00() PVPVI : Copolymer of polyvinylpyroiidone and vinylimidazole, with an average molecular weight of 20,000 QEA : bis((C2H50)(C2H40)n)(CIH3) -N~-C6H12-N+-(CH3) bis((C2H50)-(C2H40))n, wherein n = from 20 to 30 SRP 1 : Anionically end capped poly esters SRP 2 : Diethoxylated poly (1, 2 propylene terephtaiate) short block polymer PEI : Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Silicone antifoamPolydimethylsiloxane foann controller with : siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1 Opacifier : Water based monostyrene latex mixture, sold by BASF Aktiengeseilschaft under the tradename Lytron 621 Wax : Paraffin wax PA30 : Polyacryfic acid of average molecular weight of between about 4,500 - 8,000.
480N : Random copolymer of 7:3 acrylatelmethacrylate, average molecular weight about 3,500.
Polygellcarbopol: Higfi molecular weight crosslinked polyacrylates.
Metasilicate ; Sodium metasilicate (Si02:Na20 ratio = 1.0).
Nonionic : C13-C15 mixed ethoxyiated~propoxylated fatty alcohol with an average degree of ethoxyiation of 3.8 and an average degree of propoxylation of 4.5.
Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate, sold by Shell Chemical CO.
MnTACN : Manganese 1,4,7-trimethyl-1.4,7-triazacyclononane.
PAAC : Pentaamine acetate cobait(III) salt.
Paraffin : Paraffin oil sold under they tradename Winog 70 by Wintershall.
NaBz : Sodium benzoate.
BzP : Benzoyl Peroxide.
SCS : Sodium cumene sulphonate.
BTA : Benzotriazole.
pH : Measured as a 1 % solution in distilled water at 20°C.
ARP1 : Amine reaction product of 1,4-bis-(3-aminopropyl)-piperazine with a-Damascone as made from Synthesis example I
ARP2 : Amine reaction product of N,N'bis(arninopropyl)1,3-propanediamine with 8-Da~mascone as made from Synthesis example II
ARP3 : Amine reaction product of polyvinylamine MW1200 with a-Damascone as made from Synthesis example III
Clay I : Bentonite clay Clay II : Smectite clay Flocculating agent t : polyethylene oxide of average molecular weight of between 200,000 and 400,000 Flocculating agent II: polyethylene oxide of average molecular weight of between 400,000 and 1,000,000 Flocculating agent III: polymer of acrylamide ancll or acrylic acid of average molecular weight of 200,000 and 400,000 DOBS: Decanoyi oxybenzene suliFonate in the fofm of the sodium salt SRP 3 : Polysaccharide soil release polymer SRP 4 : Nonionicaily end capped poly esters The following are synthesis examples of compounds as defined in the present invention:
I-Synthesis of 1,4-bis-(3-aminopropyil~-piperazine mith a-Damascone In order to substitute both primary amine groups with .a perfume, 2eq of perfume were used for 1eq of amino functional polymer. To an ice cooled stirred solution WO 00/02982 PCT/US99/156'18 of 1 mmol of a-Damascene in 6 mL EtOH and molecular sieves {4A, 20 g), 0.5eq of 1,4-bis-(3-aminoprapyi)-piperazine was added via an addition funnel.
The reaction mixture was stirred under nitrogen atmosphere and protected from light. After the disappearance of the absorption peak from the NMR spectrum of the free perfume raw material (from 3 to 16 hours), tlhe mixture was filtrated and the solvent was removed by vacuum distillation. The yield of (i-aminoketone formation is about 90%.
Simiiar results were obtained where the a-Damasccme was replaced by Tripal, vertocitral, bourgeonal, or. citronellal. In these instances, Schiff bases are formed.
II-Synthesis of N.N'-bis(3-aminolnropyl -1,3-prouanediamine with _8-Damascone To an ice cooled solution of 1 mmol of 8-Damascene in 30 ml_ EtOH and molecular sieves (4A, 5 g), 0.5eq of the N,N'-bis(3-aminopropyl)-1,3-propanediamine was added. The reaction wa:; stirred under nitrogen atmosphere and protected from light. After 1 day, the molecular sieves and the solvent were removed by filtration and vacuum distillation respectively. ~i-Aminoketone were obtained in a 85 to 90% yield.
Similar results were obtained where the 8-Damascene was replaced by Tripal, vertocitral, bourgeonal, or citronellal. In these instances, Schiff bases are formed.
III-Synthesis of Poiyvinyiamine of MW1 Z00 with a..Damascone The following ingredients were mixed together : 0.6g of Sodium sulfate with 0.3g of polyvinylamine MW 1200 in a 10% aqueous solution and 0.3g a-Damascene.
The reaction was completed after 18 days at room temperature in the dark.
Similar results were obtained where the a-Damascene was replaced by Tripal, or citral: In these instances, Schiff-bases are formed.
In the following formulation examples all levels are quoted as % by weight of the composition unless otherwise stated, and incorporation of the amine reaction product so called herein after "ARP" in the fully formulated composition is carried out by dry addition (d), spray on (s), encapsulation in starch (es) as described in GB-1,464,616 or cyclodextrin (ec) or as is in the composition as defined herein before. The term in bracket for the ARP in the formulation examples refers to the means of incorporation. When none is provided, the incorporation is made as it is. The levels given for the ARP, whether processed or not, refer to the level of ARP as is and not to the processed ARP.
Example 1 The following high density granular laundry detergent compositions were prepared in accord with the invention:
A B C D E F G
LAS 8.0 8.0 8.0 2.0 6.0 6.0 5.0 TAS 0.5 - 0.5 1.0 0.1 1.5 C46(S)AS 2.0 2.5 - - _ -C25AS - 7.0 4.5 5.5 2.5 C68AS 2.0 5.0 7.0 - - _ 0.2 C25E5 - - 3.4 10.0 4.6 4.6 2.6 C25E7 3.4 3.4 1.0 - - - -C25E3S - - 2.0 5.0 4.5 0.5 QAS - 0.8 - - - _ -QAS (I) _ _ _ 0.8 0.5 1.0 1.5 Zeolite A 18.1 18.0 14.1 18.1 20:0 18.1 16.2 Citric acid - - 2.5 _ 2.5 1.5 Carbonate 13.0 13.0 27.0 10.0 10.0 13.0 20.6 SKS-6 - - - 10.0 _ 10.0 4.3 Silicate 1.4 1.4 3.0 0.3 0.5 0.3 Citrate - 1.0 - 3.0 - - 1.4 Sulfate 26.1 26.1 26.1 6.0 - - -Mg sulfate 0.3 - - 0.2 I - 0.2 0.03 A B C D E F G
MAIAA 0.3 0.3 0.3 4.0 1.0 1.0 0.6 CMC 0.2 0.2 0.2 0.2 0.4 0.4 0.3 PB4 9.0 9.0 5.0 - - -Percarbonat- - - - 18.0 18.0 a TAED 1.5 0.4 1.5 - 3.9 4.2 3.2 NAC-OBS - 2.0 1.0 - - -DTPMP 0.25 0.25 0.25 0.25 - -' SRP 2 - - - 0.2 0.2 -EDDS - 0.25 0.4 - 0.5 0.5 0.1 TFAA - - - _ _ - 1.1 C FAA - 1.0 - 2. 0 - -HEDP 0.3 0.3 0.3 0.3 0.4 0.4 0.3 QEA - - 0.2 - 0.5 Protease - - 0.26 1.0 - 0.3 I
Protease 0.26 0.26 1.5 1.0 Cellulase 0.3 - - 0.3 0.3 0.3 0.3 Amylase 0:1 0.1 0.1 0.4 0.5 0.5 0.1 Lipase ( 0.3 - . 0.5 0.5 0.5 0.1 1 ) Photoactivat15 15 15 - 20 20 ppm 20 ed bleach ppm ppm ppm ppm ppm (ppm) PVNOIPVP - - - 0.1 _ Brightener 0.09 0.09 0.09 - 0.09 0.09 0.01 Brightener - - - - _ _ 0:09 Perfume 0.3 0.3 0.3 0.4 0.4 0.4 0.4 spray on A B C D E F G
ARP 1 0.08(d}0.1 - - ..~~ 0.1 0.05(ec)-(es) (d}
ARP 2 - 0.08{s)0.1 (ec} 0.1 -(s}
ARP 3 (es) - - - _ _ 0.4 Silicone 0.5 0.5 0.5 '~ 0.3 0.3 0.3 antifoam Clay II 0.5 0,5 0.5 - 0.3 0.3 12.0 Flocculating0.5 0.5 0.5 - 0.3 0.3 0.3 agent Glycerol 0.5 0.5 0.5 - 0.3 0.3 0.6 Wax 0.5 0.5 0.5 0.3 0.3 0.4 Misc/minors to 100%
Density 850 850 850 850 850 85p 850 in g/litre Example 2 The following granular laundry detergent compositions A to F of particular utility under European machine wash conditions were prepared in accord with the invention:
A B C D E F
1~4S 5.5 7.5 5.0 5.0 6.0 7.0~
TAS 1.25 ~ 1.86 - 0.8 0.4 0.3 C24ASIC25AS - 2.24 5.0 5.0 5.0 2.2 C25E3S - 0.76 1.0 1.5 3.0 1.0 C45E7 3.25 - - - - 3.0 TFAA - - 2.0 - - _ C25E5 - 5.5 - - _ _ QAS 0.8 QAS ll - 0.7 1.0 0.5 1.0 0.7 STPP 19.7 - - - _ _ Zeolite A - 19.5 25.0 19.5 20.0 17.0 I ~
A B C D E F
NaSKS-6lcitric - 10.6 - 10.6 - -acid (79:21 }
NaSKS-6 - - 9.0 - 10.0 10.0 Carbonate 6.1 21.4 9.0 10.0 10.0 18.0 Bicarbonate - 2.0 7.0 5.0 - 2.0 Silicate 6.8 - 0.3 0.5 -Citrate - 4.0 4.0 - -Sulfate 39.8 - 5.0 - 12.0 Mg sulfate - - 0.1 0.2 0.2 MAIAA 0.5 1.6 3.0 4.0 1.0 1.0 CMC 0.2 0.4 1.0 1.0 0.4 0.4 PB4 5.0 12.7 - _ _ Percarbonate - - - - 18.0 15.0 TAED 0.5 3.1 - - 5.0 NAC-OBS 1.0 3.5 - - - 2.5 DTPMP 0.25 0.2 0.3 0.4 - 0.2 HEDP 0.3 - 0.3 0.3 0.3 QEA - 1.0 1.0 1.0 -Protease I - - - 0.5 1.2 -Protease 0.2fi 0.85 0.9 1.0 - 0.7 Lipase { 1 ) 0.15 0.15 0.3 0.3 0.3 0.2 Cellulase 0.28 0.28 0.2 0.2 0.3 0.3 Amylase 0.1 0.1 0.4 0.4 0.6 0.2 PVNOIPVPVI - 0.2 0.2 - -PVP 0.9 1.3 - - - 0.9 SRP 1 - - 0.2 0.2 0.2 -Photoactivated 15 27 - - 20 20 bleach (1) in ppm Photoactivated 15 - - - _ _ bleach (2) in apm Brightener 1 0.08 0.19 - - 0.09 0.15 Brightener 2 - 0.04 - - _ -_ Pertume 0.3 0.3 0.4 0.3 0.4 0.3 ARP1 0.1 1.0(ci)- - - 0.1 {es) (d}
WO 00/029$2 PCT/US99/1567$
A B C C) E P .,_ ARP2~ - 0.04(s) 0.08(ec)0.1 (d) 0.1 (es) Silicone antifoam0.5 2.4 0.3 0.5 0.3 2.0 Minorslmisc to 100%
Density in g/litre750 750 750 T50 750 750 Example 3 The following detergent formulations of particular utility under European machine wash conditions were prepared in accord with the invention.
A __ Blown powder LAS 6.0 5.0 11.0 6.0 TAS 2.0 - - 2,0 Zeolite A 24.0 - - 20.0 STPP - 27.0 24.0 -Sulfate 4.0 6.0 13.0 -MAIAA 1.0 4.0 6.0 2.0 Silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.2 0.2 Silicone antifoam 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray on Brightener 0.02 - - 0.02 C45E7 - - - 5.0 C45E2 2.5 2.5 2.0 -C45E3 2.6 2.5 2.0 -Pertume 0.5 0.3 0.5 0.2 Silicone antifoam 0.3 0.3 0.3 -Dry additives QEA ( - - - 1.0 EDDS I 0.3 - _ Sulfate 2.0 3.0 5.0 10.0 A B C D
Carbonate 6.0 13.0 15.0 14.0 Citric acid 2.5 - - 2.0 QAS f 1 0.5 - - 0. 5 SKS-6 10.0 - - -Percarbonate 18.5 - - -PB4 - 18.0 10.0 21.5 TAED 2.0 2.0 - 2.0 NAC-OBS 3.0 2.0 4.0 -Protease 1.0 1.0 1.0 1.0 Lipase - 0.4 - 0.2 Lipase (1} 0.4 - 0.4 Amylase 0.2 0.2 0.2 0.4 Brightener 1 0.05 - - 0.05 ARP3 0.03 0.1 (es) 1.0 0.1 0.05(ec) Misclminor to 100%
Example 4 The following granular detergent formulations were prepared in accord with the invention.
A B _C D E F
Blown powder LAS 23.0 8.0 7.0 9.0 7.0 7.0 TAS - - - - 1.0 -C45AS 6.0 6.0 5.0 8.0 - -C45AES - 1.0 1.0 1.0 - -C45E35 - - - - 2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MAIAA - 0.5 - - - 2.0 MAIAA ('! ) 7.0 - _ _ _ _ AA - 3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 14.3 11.0 15.0 19.3 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 A B C D E F
Carbonate 15.0 20.0 10.0 20.7 8.0 6.0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA - 0.9 0.5 - - 0.5 Brightener 2 0.3 0.2 0.3 - 0.1 0.3 Spray on C45E7 - 2.0 - - 2.0 2.0 C25E9 3.0 - - - - -C23E9 - - 1.5 2.0 - 2.0 Perfume 0.3 0.3 0.3 2.0 0.3 0.3 ARP2 0.1 0.05(s) - - -{s) Agglomerates C45AS - 5.0 5.0 2.0 - 5.0 BAS - 2.0 2.0 - - 2.0 Zeolite A - 7.5 7.5 8.0 - ?.5 Carbonate - 4.0 4.0 5.0 - 4.0 PEG 4000 - 0.5 0.5 - - 0.5 Misc (water etc) - 2.0 2.0 2.0 - 2.0 Dry additives QAS (I) - _ _ - 1.0 -Citric acid - - - - 2.0 -PB4 - - - - 12.0 1.0 PB1 4.0 1.0 3.0 2.0 - -Percarbonate - - - - 2.0 10.0 Carbonate - 5.3 1.8 - 4.0 4.0 NOBS 4.0 - 6.0 - - 0.6 Methyl cellulose 0.2 - - - - -SKS-6 8.0 - - - - -STS - - 2.0 - 1.0 -Cumene sulfonic acid- 1.0 - - - 2.0 Lipase 0.2 - 0.2 - 0.2 0.4 Cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase 0.2 - 0.1 - 0.2 -Protease 0.5 0.5 0.5 0.3 0.5 0.5 WO 00/029$2 PCTIUS99/15678 A B C D E F
PVPVI - - - - 0.5 0.1 PVP _ - _ _ 0.5 PVNO - 0.5 0.3 - -QEA - - - - 1.0 -SRP1 0.2 0.5 0:3 - 0.2 ARP2 0.1 0.2 0.04(d) 0.02 0.01 0.02(es) (es) Silicone antifoam 0.2 0.4 0.2 0.4 0.1 -Mg sulfate - - 0.2 - -0.2 Misc/minors to 100%
G H I J
Blown powder Clay I or ll 7.0 10.0 6.0 2.0 LAS 16.0 5.0 11.0 6.0 TAS - 5.0 ~- 2.0 Zeolite A - 20.0 ~- 10.0 STPP 24.0 - 14.0 -Sulfate - 2.0 .- -MA/AA - 2.0 1.0 1.0 Silicate 4.0 7.0 3.0 -CMC 1.0 X0.5 0.6 Brightener 1 0.2 0.2 X0.2 0.2 Carbonate 10.0 10.0 20.0 -DTPMP 0.4 0.4 iD.2 Spray on Brightener 1 0.02 - ~- 0.02 C45E7 or E9 - - ;2.0 1.0 C45E3 or E4 - - 2.0 4.0 Perfume 0.5 - 0.5 0.2 Silicone antifoam 0.3 - .. _ Dry additives Flocculating agent 0.3 1.0 1.0 0.5 I or il ~
QEA - _ - 1.0 HEDP/ EDDS 0.3 -Sulfate 2.0 - - -Carbonate 20.0 13.0 15.0 24.0 Citric acid 2.5 - - 2:0 QAS - - Cl.S 0.5 NaSKS-6 3.5 - - 5.0 Percarbonate - - - 9.0 PB4 - - i.0 NOBS - - - 1.3 TAED - - c!.0 1.5 Protease 1.0 1.0 1.0 1.0 Lipase - 0.4 - 0.2 Amylase 0.2 0.2 C1.2 0.4 Brightener 2 0.05 - - 0.05 Perfume 1.0 0:2 C).5 0.3 Speckle 1.2 0.5 ~ 2.0 -ARP1 0.08 1.5 (d) 0.2 0.05 ARP2 3.0(d) 0.6 C).2 0.1 Misc/minor to 100%
Exam,~~le 5 The following nii bleach-containing detergent formulations of particular use in the washing of coloured clothing, according to the present invention were prepared:
A B C
Blown Powder Zeolite A 15.0 15.0 -Sulfate 0.0 5.0 -LAS 3.0 3.0 DTPMP 0.4 0.5 -CMC 0.4 0.4 -MAlAA 4.0 4.0 -Agglomerates C45AS - - 11.0 A B C
LAS 6.0 _ -5.0 TAS 3.0 2.0 -Silicate 4.0 4.0 -Zeolite A 10.0 15.0 13.0 CMC - - 0,5 MAIAA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfume 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2,0 ARP2 0.08(s) - -Dry additives M~~ - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - g,0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 ARP1 0.05 0.08 0.1 (es) Silicone antifoam 5.0 5.0 5.0 Dry additives Sulfate 0.0 9.0 0.0 Misclminors to 100% 100.0 100.0 100.0 Density (g/litre) 700 700 700 Example 6 The following granular detergent formulations were prepared in accord with the invention.
Base granule Zeoiite A 30.0 22.0 24.0 10.0 Sulfate 10.0 5.,0 10.0 7.0 MA/AA 3.0 ~- - -AA - 1..6 2.0 _ MAIAA ( 1 } - 12 .0 - 6.0 LAS 14.0 1CL0 9.0 20.0 C45AS 8.0 7..0 9.0 7.0 C45AES - 1..0 1.0 -Silicate - 1..0 0.5 10.0 Soap - 2..0 -Brightener 1 0.2 0..2 0.2 0.2 Carbonate 6.0 9..0 10.0 10.0 PEG 4000 - 1..0 1.5 -DTPA - 0.,4 - -Spray on C25E9 - .. _ 5,0 C45E7 1.0 1.0 - -C23E9 - 1,0 2.5 -Perfume 0.2 0.3 0.3 -ARP2 0:04(s) -~ - -Dry additives Carbonate 5.0 10.0 18.0 8.0 PVPVI/PVNO 0.5 -~ 0.3 -Protease 1.0 1.0 1.0 0.5 Lipase 0.4 -~ - 0.4 Amylase 0.1 -. - 0.1 Celiuiase 0.1 0.2 0.2 0.1 Noes - a.a - 4.5 PB1 1.0 5.0 1.5 6.0 Sulfate 4.0 5.0 - 5.0 SRPI - 0.4 - _ fi5 ___ A 8 C D
ARP1 0.05 O.CI8 0.1(es) -~
ARP2 0.05 - - 0.02(es) Sud supressor - 0..5 0.5 -Misc/minor to 100%
Example 7 The following granular detergent compositions were prepared in accord with the invention.
A B
T- C
Blown powder _ Zeolite A 20.0 - 15.0 STPP - 20.0 -Sulphate - - 5.0 Carbonate - - 5.0 TAS - - 1.t) LAS 6.0 6.0 6.0 C68AS 2.0 2.0 -Siiicate 3.0 8.0 -MA/AA 4.0 2.0 2.0 CMC O.fi 0.6 i 0.2 Brightener 1 0.2 0.2 0.'I
DTPMP 0.4 0.4 t 0.'I
STS - - 1.0 Spray on C45 E7 5.0 5.0 ~ ~ 4.0 Silicone antifoam 0.3 0.3 I 0.'i Perfume 0.2 0.2 0.3 ARP1 0.1 (s) 0.05(s) 0.08(s) Dry additives 1. () Carbonate 14.0 9.0 ' 10.0 PB1 1.5 2.0 i -PB4 '18.5 13.0 a 13.0 A B C.
TAED 2.0 2.0 2.0 QAS (I) - - 1.0 Photoactivated bleach15 ppm 15 ppm l5ppm SKS-6 - - 3.0 Protease 1.0 1.0 0.2 Lipase 0.2 0.2 0.2 Amylase 0.4 0.4 0.2 Cellulase 0.1 0.1 0.2 Sulfate 10.0 20.0 5.0 Misclminors to 100%
Density {g/litre) 700 700 7CE0 Example 8 The following detergent compositions, according to the present invention were prepared:
A B C
Blown Powder _._ Zeolite A 15.0 15.0 15.0 Sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DTPMP 0.4 0.2 0.4 EDDS - 0.4 0.2 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On A B C
Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 -ARP2 0.02(s) - -Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 -Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 PEO - - 0.2 ARP1 0.1 0.2 0.08(ec) Bentonite clay - - 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 Misclminors to 100% 100.0 1100.0 100.0 Density (g/litre) 850 850 850 D E F G H
Blown Powder STPPI Zeolite 9.0 15.0 15.0 9.0 9.0 A
Flocculating 0.5 0.2 0.9 1.5 -agent II
or III
LAS 7.5 23.0 3.0 7.5 7.5 QAS 2.5 1.5 - - -DTPMP 0.4 0.2 0.4 0.4 0.4 HEDP or EDDS - 0.4 0.2 - -CMC 0.7 0.4 0.4 0.1 0.1 Sodium carbonate _ 20.0 20.0 10.0 5.0 Brightener 0.05 - - 0.05 0.05 Clay I or II - 10.0 - - -STS 0. 5 _ - 0.5 0.
MA/AA 1.5 2.0 2.0 1.5 1.5 Agglomerates Suds suppresser 1.0 1.0 - Z.0 0.5 (silicon) Agglomerate Clay 9.0 - - 4Ø 10.0 Wax 0.5 - - 0.5 1.5 Glycerol 0.5 - - 0.5 0.5 Agglomerate ~S - 5.0 5.0 - _ TAS - 2.0 1.0 - -Silicate 3.0 4.0 - -Zeolite A - 8.0 8.0 -Carbonate - g,0 4,0 _ -Spray On Perfume 0.3 - - 0.3 0.3 C45E7 or E9 2.0 - - 2.0 2.0 C25E3 or E4 2.0 - - 2.0 2.0 Dry additives Citrate or citric2.5 - 2.0 2.5 2.5 acid Clay I or II - 5.0 5.0 -Flocculating agent - - - 0.2 l or II
Bicarbonate - 3.0 - - -Carbonate 15.0 - - 25.0 31.0 TAED 1.0 2.0 5.0 1.0 -Sodium perborate 6.0 7.0 10.0 6.0 or percarbonate SRP1,2,3or4 ~ 0.2 0.1 0.2 0.5 0.3 ~ ~ ~
CMC or nonionic 1.0 1.5 0.5 - -ceflulose ether Protease 0.3 1.0 1.0 0.3 0.3 Lipase - 0.4 0.4 -Amylase 0.2 0.6 0.6 0.2 0.2 Cellulase 0.2 0.6 0.6 0.2 0.2 Silicone antifoam- 5.0 5.0 - -Perfume (starch) 0.2 0.3 1.0 0.2 0.2 Speckle 0.5 0.5 0.1 _ 1.0 -NaSKS-6 (silicate3.5 - -3.5 2R) Photobleach 0.1 - - 0, ~ 0,1 Soap 0.5 2.5 - 0.5 0.5 Sodium sulfate - 3.0 - -ARP1 0.1 1.0(d)0.05 3.0(e:>)0.09 Misc/minors to 100.0 100.0 100.0 100.0 100.
100% 0 Density (g/litre)850 850 850 850 850 Example 9 The following detergent formulations, according to i;he present invention were prepared:
A B C D
LAS 18.0 14.0 :?4.0 20.0 QAS 0.7 1.0 _ 0.7 TFAA - 1.0 - -C23E56.5 - - 1.0 _ C45E7 - 1.0 C45E3S 1.0 2.5 1.0 STPP 32.0 18.0 30.0 22.0 Silicate 9.0 5.0 9.0 8.0 Carbonate 11.0 7.5 10.0 5.0 Bicarbonate - ! 7,5 1 _ _ ~
A B C D
PB1 3.0 1:0 - -PB4 - 1.0 -NOBS 2.0 1.0 - -DTPMP - 1.p _ DTPA 0.5 - 0.2 0.3 SRP 1 0.3 0.2 - 0.1 MAIAA 1. 0 1: 5 2 . 0 - -0. 5 CMC 0.8 0.4 0.4 0.2 PEI - - 0.4 -Sodium sulfate20.0 10.0 x'Ø0 30.0 Mg sulfate 0.2 0.4 0.9 Protease 0.8 1.0 0.5 0:5 Amylase 0.5 0:4 - 0.25 --Lipase 0.2 - X0.1 _ Cellulase 0.15 - - 0.05 Photoactivated30ppm 20ppm - lOpp,r bleach (ppm) ARP3 0.04(s) 0.08(ec) 0..1 (s) 0.04(es) Perfume spray 0.3 0:3 X0.1 0.2 on Brightener 0.05 0.2 0.08 0.1 1l2 Misclminors to 100%
Example 10 The following liquid detergent formulations were prepared in accord with the invention (levels are given as parts per weight}.
A B C D
~S 11.5 8.8 - 3.9 -C25E2.5S - 3.0 18.0 - 16.0 C45E2.25S 11.5 3.0 - 15.7 -C23E9 - 2.7 1.8 2.0 1.0 C23E7 3:2 - _ CFAA - - 5.2 - 3.1 TPKFA 1.6 - 2.0 0.5 2.0 Citric acid (50%} 6.5 1.2 2.5 4.4 2.5 Calcium formate 0.1 0.06 0.1 -Sodium formate 0.5 0.06 0.1 0.05 0.05 Sodium cumene sulfonate4.0 1.0 3.0 1.18 Borate 0.6 - 3.0 2.0 2.9 Sodium hydroxide 5.8 2.0 3.5 3.7 2.7 Ethanol 1.75 1.0 3.6 4.2 2.9 1, 2 propanediol 3.3 2.0 8.0 7.9 5.3 Monoethanolamine 3.0 1.5 1.3 2.5 0.$
TEPAE 1.6 - 1.3 1.2 1.2 Protease 1.0 0.3 1.0 0.5 0.7 Lipase - - 0.1 Cellulase - - 0.1 0.2 0.05 Amylase _ _ _ 0.1 SRP1 0.2 - 0.1 -DTPA - - 0.3 -PVNO - - 0:3 - 0.2 ARP1 0.3 - - 0.1 _ ARP2 - 0.04 - -0.1 ARP3 - - i0.3 -Brightener 1 0.2 0.07 0.1 - _ Silicone antifoam 0.04 0.02 0.1 0.1 0.1 Water/minors Example 11 The following liquid detergent formulations were prepared in accord with the invention (levels are given in parts per weight):
A B C 'D E F G H
LAS 10.0 '! 9.0 - 25.0 - - -3.0 C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0 C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0 C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0 TFAA _ _ ~ 4.5 _ 6.0 8.0 8.0 APA - 1.4 - - 3.0 1.0 2.0 -TPKFA 2.0 - 13.0 _ - 15.0 11.0 11.0 7.0 Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 Dodecenylltetradecenyl12.0 10.0 - - 15.0 - - -succinic acid Rape seed fatty acid4.0 2.0 1.0 - 1.0 - 3.5 -Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 1 3.0 Monoethanolamine - - - 5.0 - - 9.0 _ 9.0 Triethanolamine - - 8.0 _ - _ - -TEPAE 0.5 - 0.5 0.2 - - 0.4 0.3 DTPM P 1.0 1. 0. 1. 2.0 1.2 1. -Protease ~ 0.5 0.5 0.4 0.25 - 0.5 0.3 0.6 Alcalase - - - - 1.5 - - -Lipase - 0.10 - 0.01 - - 0.15 0.15 Amylase 0.25 0:25 0.6 0.5 0.25 0.9 0.6 0.6 Cellulase - - - 0.05 - - 0.15 0.15 Endolase - - - 0.10 - - 0.07 -SRP2 0.3 - 0.3 0.1 - - 0.2 0.1 Boric acid 0.1 0.2 1.0 2.0 1.0 1.5 2.5 2.5 Calcium chloride - 0.02 - 0.01 - - - -Bentonite clay - - - - 4.0 4.0 - -~
Brightener 1 - 0.4 - - 0.1 0.2 0.3 -~
WO 00!02982 PCTIUS99/15678 A B C D E F G H
Sud supressor 0.1 0.3 - 0.1 0.4 - - -Opacifier 0.5 0.4 - 0.3 0.8 0.7 - -ARP1 0.3 - 0.1 - 0.05 - 0.1 0.08 ARP2 - 0.04 - 0.02 - 0.1 0.08 0.1 Water/minors NaOH up to pH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 Example 12 The following liquid detergent compositions were prepared in accord with the invention (levels are given in parts per weight).
A B
~S _ 18. g .. 27.6 C45AS 13.8 5.9 C13E8 3.0 3.1 Oleic acid 3.4 2.5 Citric acid 5.4 5.4 Sodium hydroxide 0.4 3.6 Calcium formate 0,2 0.1 Sodium formate _ 0.5 Ethanol 7.0 _ Monoethanolamine 16.5 ~ 8.0 1,2 propanediol 5.9 5.5 Xylene sulfonic acid - 2.4 TEPAE 1.5 0.8 Protease 1.5 0.6 PEG - 0.7 Brightener 2 0.4 0.1 Perfume spray on 0.5 0.3 ARP1 0.3 -ARP3 - 0.04 WateNminors Example 13 The following is a composition in the form of a tablet, bar, extrudate or granule in accord with the invention A B C D E ~E ~r , Sodium C11-C13 12.0 16.0 23.0 191.0 18.0 20.0 16.0 alkylbenzenesulfonate Sodium C14-C15 alcohol 4 -. - - 4.0 sulfate C,d-C..s alcohol ethoxyfate- - 2.0 - 1.0 1.0 1.0 (3) suifate .-Sodium C14-C15 alcohol2 2 - 1 0 0 ' . . . - - 5.0 , ethoxylate CQ C.r, alkyl dimethyl - - 1.0 0.5 2.0 hydroxy ethyl quaternary ammonium salt Tallow fatty acid _ - - - 1.0 Sodium tripolyphosphate23.0 25.0 14.0 22,0 20.0 10.0 20.0 I
Zeo I ite Sodium carbonate 25.0 22.0 35.0 20.0 28.0 41.0 30.0 Sodium Polyacrylate 0.5 0.5 0.5 _ - - _ O.:i (45%) Sodium - - 1.0 1.CI 1.0 2.0 0.5 poiyacrylatelmaieate polymer Sodium silicate (1:6 3.0 6.0 9.0 8.0~ 9.0 6.0 8.0 ratio NaOISi02)(46%) Sodium sulfate - - - - - 2.0 3.0 Sodium perborate/ 5.0 5.0 10.0 - 3.0 1.0 -percarbonate Poly(ethyleneglycol), 1.5 1.5 1.0 1.0 - - 0.5 MW
w4000 (50%) Sodium carboxy methyl 1.0 1.0 1.0 - 0.5 0.5 0.5 cellulose NOBSI DOBS ~ - 1.0 ~ 1.0 0.7 -WO 0'0/02982 PCT/US99/15678 TAED 1.5 1.0 2.5 - 3.0 0.7 -SRP 1 1.5 1.5 1.0 1.0 - 1.0 -Clay I or I I 5.0 6.0 12.0 7, 0 10.04.0 3.0 Flocculating agent 0.2 0.2 3.0 2.0 0.1 1.0 0.5 I or fll Humectant 0.5 1.0 0.5 1..0 0.5 0.5 -Wax 0.5 0.5 1.0 - - 0.5 0.5 Moisture 7.5 7.5 6.0 7..0 5.0 3.0 5.0 Magnesium sulphate - - _ _ _ 0.5 1.5 Chefant - _ _ _ 0.8 0.6 1.0 Enzymes, including - - - - 2.0 1.5 2.0 amylase, cellulase.
protease and lipase ARP2 0.3 3.0(dj- - - _ _ ARP1 0.08 0.1 3.0(d)1.5(es)0.051.0(d) 0.05 Speckle 2.5 4..1 4.2 4.4 5.6 5.0 5.2 minors, e.g. perfume, 2.0 1.0 1.0 1.0 2.5 1.5 1.0 PVP, PVPVI/PVNO, brightener, photo-bleach.
H 1 _I a Sodium C11-C13 23.0 13.0 20.0 18.0 alkylbenzenesuifonate Sodium C14-C15 alcohol sulfate _ 4.0 - -Clay I or I! 5.0 10.0 14.0 6.0 Flocculating agent I or il 0.2 0.3 0.1 0.9 Wax 0.5 0.5 1.0 -Humectant (glyceroil silica) 0.5 2.0 1.5 -C,~-C,~ alcohol ethoxylate sulfate- _ .0 Sodium C14-C15 alcohol ethoxylate2.5 3.5 -( C~-C,4 alkyl dimethyl hydroxy - - 0.5 ethyl quaternary ammonium salt Tallow fatty acid 0.5 - - _ Tallow alcohol ethoxylate (50) - - 1.3 Sodium tripolyphosphate - 4 - 20.0 1.0 Zeolite A, hydrate (0.1-10 micron26.3 _ 21.3 -size) -Sodium carbonate 24.0 22.0 35.0 27.0 Sodium Polyacrylate (45%) 2.4 - 2.7 -Sodium polyacrylate/maleate polymer- - 1.0 2.5 Sodium silicate (1.6 or 2 or 4.0 7.0 2.0 6.0 2.2 ratio NaO/Si02)(46%) Sodium sulfate - 6.0 2.0 -Sodium perboratel percarbonate 8.0 4.0 - 12.0 Poly(ethyleneglycol), MW 4000 1.7 0.4 1.0 -(50%) Sodium carboxy methyl cellulose 1.0 - - 0.3 Citric acid _ _ 3.0 _ NOBSI DOBS 1.2 - - 1.0 TAED 0.6 1.5 - 3.0 Perfume 0.5 1.0 0.3 0.4 SRP 1 - 1.5 1.0 1.0 Moisture 7.5 3.1 6.1 7.3 Magnesium sulphate - _ _ 1.0 Chelant _ _ _ 0.5 speckle 1.0 0.5 0.2 2.7 Enzymes, including amylase. celiulase.- 1.0 - 1.5 protease and lipase ARP1 0.1 3.0(CI)1.0(es)0.3 minors. e.g. brightener, photo-bleach1.0 1.0 1.0 1.0 Example 14 The following laundry bar detergent compositions weire prepared in accord with the invention (levels are given in parts per weight).
A B C D . E F G H
~S - - 19.0 15.0 21.0 6.75 8.8 C28AS 30.0 13.5 - - - 15.75 11.2 22.5 Sodium laurate2.5 9.0 - - _ _ _ -Zeoiite A 2.0 1.25 - - ~ 1:25 1.25 . 1 .25 Carbonate 20:0 3.0 13.0 8.0 10.0 15.0 15.0 _ 10.0 Calcium 27.5 39.0 35.0 - - 40.0 - 40.0 carbonate A B C D E: F G H
Sulfate 5.0 5.0 3.0 5.0 3.0 - - 5.0 TSPP 5.0 - - - -~ 5.0 2.5 -STPP 5.0 15.0 10.0 - -~ 7.0 8.0 10.0 Bentonite clay- 10.0 - - 5.0 _ _ _ DTPMP - 0.7 0.6 - 0.6' 0.7 0.7 0.7 CMC - 1.0 1.0 1.0 1.0 - - 1.0 Talc - - 10.0 15.0 10.0 - - -Siiicate - - 4.0 5.0 3.0 - - -PVNO 0.02 0.03 - 0.01 - 0.02 - -MA/AA 0.4 1.0 - - 0.2 0.4 0.5 0.4 SRP1 0.3 0.3 0:3 0.3 0.3 0.3 0.3 0.3 Protease - 0.12 - 0.08 O.t)8 - - 0.1 Lipase - 0.1 - 0.1 - - - _ Amylase _ - 0.8 - - - 0.1 -Celluiase - 0.15 - - 0.1i 0.1 - -PEO - 0.2 - 0.2 0.3 _ - 0 3 Perfume 1.0 0.5 0.3 0.2 0.~4 - - 0.4 Mg sulfate - - 3.0 3.0 3.~0 - - -ARP1 0.3 - - 0.04 - 0.5 - -ARP2 - 0.04 - - 0.1 - 0.08 _ ARP3 - - 0.3 - - - - 0.3 Brightener 0.15 0.10 0.15 - - - - 0.1 Photoactivated- 15.0 15.0 15.0 15..0 - - 15.0 bleach (ppm) Example 15 The following detergent additive compositions were prepared according to the present invention A B C
~S - 5.0 5.0 STPP 30.0 - 20.0 Zeolite A _ 35.0 20.0 PB1 ~ 20.0 15.0 -ii;
A B C
TAED 10.0 8.0 _ ARP 1 0.3 - 0.1 ARP2 - 0.04 0.02 Protease - 0.3 0.3 Amylase - 0.06 0.06 Minors, water and rnisceilaneous Up to 100%
Example 16 The following compact high density (0.96Kgll;l dishwashing detergent compositions were prepared according to the present invention A B C D E F G H
STPP - - 54.3 51.4 51.4 - - 50,g Citrate 35.0 17.0 - - - 46.1 40.2 Carbonate - 17.5 14.0 14.0 14.0 - 8.0 32.1 Bicarbonate - - - - - 25.4 - _ Silicate 32.0 14.8 14.8 10.0 10.0 i .0 25.0 3.1 Metasilicate- 2.5 - 9.0 9.0 - - _ PB1 1.9 9.7 7.8 7.8 7.8 - -PB4 8.6 - _ _ _ _ _ _ Percarbonate- - - - - 6.7 11.8 4.8 Nonionic 1.5 2.0 1.5 1.7 1.5 2:6 1.9 5.3 TAED 5.2 2:4 - - - 2.2 - 1.4 HEDP - 1.0 - _ _ _ _ DTPMP - 0,6 _ _ _ - _ -MnTACN - _ _ _ _ _ 0.008 _ PAAC - - 0.008 0.01 0.00T _ _ _ BzP _ _ _ - 1.4 - _ _ Paraffin 0.5 0.5 0.5 0.5 0.5 0.6 - -ARP3 0.1 0.3 0.2 0.05 - - - O.g ARP1 - - - - 0.3 0.03 0.5 -Protease 0.072 0.072 0.029 0.053 0.046 0.026 0.059 0.06 Amylase 0.012 0.012 0.006 0.012 0.013 0.009 0.017 0.03 Lipase - 0.001 - 0.005 - - - _ BTA 0.3 0.3 0.3 0.3 0.3 - 0.3 0.3 I ~;
A B C D E F G H
~
- _ _ _ _ - 4.2 _ MAIAA
480N 3.3 - 6.0 _ _ _ _ _ 0.9 Perfume 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1 Sulphate 7.0 20.0 5.0 2.2 0.8 12.0 4.6 -pH 10.8 11.0 10.8 11.3 11.3 9.6 10.8 10.9 Miscellaneous and Up to '100%
water Exama~le 77 The following granular dishwashing detergent compositions of bulk density 1.02Kg/L were prepared according to the present invention A B C D E F G H
STPP 30.0 30.0 33.0 34.2 29.6 31.1 26.6 17.6 Carbonate 30.5 30.5 31.0 30.0 23.0 39.4 4.2 45.0 Silicate 7.4 7.4 7.5 7.2 13.3 3.4 43.7 12.4 Metasiiicate- - 4.5 5.1 - - - _ Percarbonate- - - - - 4.0 -PB1 4.4 4.2 4.5 4.5 - - - -NADCC - - - - 2.0 - 1.6 1.0 Nonionic 1.2 1.0 0.7 0.8 1.9 0.7 0.6 0.3 TAED 1.0 - - - _ O,g _ _ PAAC - 0.004 0.004 0.004 - - - -BzP - _ - 1.4 - _ _ Paraffin 0.25 0.25 0.25 0.25 - - - -ARP3 0.3 0.1 0.8 0.2(es} - - 0.1 (ec)0.2 (ec) ARP 1 - - - - 0.3 0.1 0.1 (ec)0.2 {ec) Protease 0.036 0.015 0.03 0.028 - 0.03 - -Amyiase 0.003 0.003 0.01 0.006 - 0.01 - -Lipase 0.005 - 0.001 - - - _ _ BTA 0.15 0.15 0.15 0.15 - - - _ Perfume 0.2 0.2 0.2 0.2 0.1 0.2 0.2 -Sulphate 23.4 25.0 22.0 18.5 30.1 19.3 23.1 23.6 pH 10.8 10.8 11.3 11.3 10.7 11.5 12.7 10.9 Miscellaneous Up to 100%
and water ii.
Example 18 The following tablet detergent compositions were prepared according to the present invention by compression of a granular dishwashing detergent composition at a pressure of 13KNIcm2 using a standard 12 head rotary press:
A B C D E F
STPP - 48.8 49.2 38.0 - 46.8 Citrate 26.4 - - = 31.1 -Carbonate - 5.0 14.0 '15.4 14.4 23.0 Silicate 26.4 14.8 15.0 '12.6 17.7 2.4 , ARP1 0.3 - - - 0.06 -ARP2 - 0.04 - - - 0.08 ARP3 - - 0.3 0.1 (ec)-Protease 0.058 0.072 0.041 0.033 0.052 0.013 Amylase 0.01 0.03 0.012 0.007 0.016 0.002 Lipase 0.005 - - - - _ PB 1 1.6 7.7 12.2 110.6 15.7 -PB4 6.9 - - - - 14.4 Nonionic 1.5 2.0 1.5 11.65 0.8 6.3 PAAC - - 0.02 0.009 -MnTACN - - - - 0.007 -TAE D 4.3 2.5 - - 1.3 1.8 HEDP 0.7 - - 0.7 - 0.4 DTPMP 0.65 - - - - _ Paraffin 0.4 0.5 0.5 0.55 - -BTA 0.2 0.3 0.3 ~0.3 -PA30 3.2 - _ _ _ _ MAIAA _ _ _ - 4.5 0.55 Perfume - - 0.05 Cl.05 0.2 0.2 Sulphate 24.0 13.0 2.3 - 10.7 3.4 Weight of tablet25g 25g 20g 30g 18g 20g pH 10.6 10.6 10.7 10.7 10.9 11.2 Miscellaneous water Up to 1100%
and _ g1 Example 19 The following liquid dishwashing detergent compositions of density 1.40Kg/L
were prepared according to the present invention A B C D
STPP 17.5 17.5 17.2 16.0 Carbonate 2.0 - 2.4 -Sificate 5.3 6.1 14.6 15.7 NaOCI 1.15 1.15 1.15 1.25 Polygen/carbopol 1.1 1.0 1.1 1.25 Nonionic - - 0.1 NaBz 0.75 0.75 - -ARP3 0.3 0.5 0.05 0.1 NaOH - 1.9 - 3.5 KON 2.8 3.5 3.0 -pH 11.0 11.7 10.9 11.0 Sulphate, miscellaneousand water up to 00%
Example 20 The following liquid rinse aid compositions were prepared according to the present invention A B C
Nonionic 12.0 - 14.5 Nonipnic blend - 64.0 Citric 3.2 - fi.5 HEDP 0.5 - -PEG - 5.0 _ SCS 4.8 - 7.0 Ethanol 6.0 8.0 -ARP'f 0.3 - 0,1 ARP2 - 0.04 0.01 pH of the liquid 2.0 7.5 I
Miscellaneous and Up to 1100%
water II
Example 21 The following liquid dishwashing compositions were prepared according to the present invention A B C D E
C17ES 28.5 27.~G 19.2 34.1 34.1 Amine oxide 2.6 5.0 2.0 3.0 3.0 C12 glucose amide - - 6,p _ Betaine 0.9 - - 2.0 2.0 Xylene sulfonate 2.0 4.0 - 2.0 -Neodol C11E9 - - 5.0 - -Polyhydroxy fatty acid amide- - - 6.5 6.5 Sodium diethylene penta acetate- - 0.03 - -(40%) TAED - - - 0.06 0.06 Sucrose - - - 1.5 1.5 Ethanol 4.0 5.5 5.5 9.1 9.1 Alkyl diphenyl oxide disulfonate- - - - 2.3 Ca formate - - - 0.5 1.1 Ammonium citrate 0.06 0.1 - - -Na chloride - 1.0 - - -Mg chloride 3.3 - 0.7 - -Ca chloride - - 0.4 - -Na suffate - - 0.06 -Mg sulfate O,Og _ _ _ _ Mg hydroxide - - - 2.2 2.2 Na hydroxide - - - 1.1 1.1 Hydrogen peroxide 200ppm 0.16 0.006 - -ARP3 0.3 - 0.1 - 0.1 ARP'! - 0.3 - 0.1 0.1 Protease 0.017 0.005 .0035 0.003 0.002 Perfume 0.18 0.09 0.09 0.2 0.2 Water and minors Up to 100%
i', Example 22 The following liquid hard surface cleaning compositions were prepared according to the present invention A B C. D E
ARP2 0.04 - 0.08 - 0.01 ARP3 - 0.3 - 0.125 0.1 Amylase 0.01 0.002 0.005 - -Protease 0.05 0.01 0.02 - -Hydrogen peroxide - - - 6.0 6.8 Acetyl triethyl citrate- - - 2.5 -DTPA - - - 0.2 -Butyl hydroxy toluene- - - 0.05 -EDTA* 0.05 0.05 O.E)5 -Citric l Citrate 2.9 2.9 2.9 1.0 -LAS 0.5 0.5 0.5 - -C 12 AS 0.5 0.5 0. 5 - -C 1 OAS - - - - 1.7 C12(E)S 0.5 0.5 0.5 - -C12,13 E6.5 nonionic 7.0 7.0 7.0 - -Neodol23-6.5 - - - 12.0 -Dobanol23-3 - - - - 1.5 Dobanol91-10 - - - - 1.6 C25AE1.8S - _ - 6.0 Na paraffin sulphonate- - - 6.0 Perfume 1.0 1.0 1.0 0.5 0.2 Propanediol - - - 1.5 Ethoxylated tetraethylene- - - 1.0 -pentaimine 2, Butyl octanol - - - - 0.5 Hexyl carbitol** 1.0 1.0 1.0 - -SCS 1.3 1.3 1.3 - -pH adjusted to 7-12 7-12 7-12 4 -Miscellaneous and Up to 100%
water *Na4 ethylenediamine diacetic acid *Diethylene glycol monohexyt ether i i, Example 23 The following spray composition for cleaning of hard surfaces and removing household mildew was prepared according to the present invention ARP2 0.04 Amylase 0.01 Protease 0.01 Na octyl suifate 2.0 Na dodecyi sulfate 4.0 Na hydroxide 0.8 Silicate 0.04 Butyl carbitol* 4.0 Perfume 0.35 Waterlminors up to 100~0 *Diethylene glycol monobutyl ether Example 24 The following lavatory cleansing block compositions were prepared according to the present invention.
A B C
C16-18 fatty alcoho1l50E0 80.0 - -~S - - 80.0 Nonionic - 1.p Oleoamide surfactant - 26:0 -Partially esterified copolymer of vinylmethyl5.(1 - -ether and malefic anhydride, viscosity 0.1-0.5 Polyethylene glycol MW 8000 - 39.0 -Water-soluble K-polyacrylate MW 4000-8000 - 12.0 -Water-soluble Na-copolymer of acryiamide - 19.0 (70%) and acryciic acid (30%) low MW
Na triphosphate 10.0 - -Carbonate - _ g.0 ARP2 0Ø4 - 0.01 ARP3 - 0.25 0.1 A B C
Dye 2.;i 1.0 1.0 Perfume 3.0 - 7.0 KOH J HCL solution pH 6-11 Example 25 The following toilet bowl cleaning composition was prepared according to the present invention.
A B
C14-15 linear alcohol 7E0 2.0 10.0 Citric acid 10.0 5.0 ARP2 0.04 -ARP3 - 0.1 DTPMP - 1.0 Dye 2.0 1.0 Perfume 3.0 3.0 NaOH
pH Ei-11 Water and minors Up to 100%
cyclopentadecanolide;
16-hydroxy-9-hexadecenoic acid lactose; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyicyclopenta-gamma-2-benzopyrane; ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1 b]furan; cedrol; 5-(2;2,3-trimethylcyclopent-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3~-cyciopenten-1-yl)-2-buten-1-0l; caryophyllene alcohol; cedryl acetate: para-tert-butylcyclohexyl acetate;
patchouli; olibanum resinoid; labdanum; vetivert; copaiba balsam; fir balsam;
and condensation products of: hydroxycitronellal and methyl anthranilate;
hydroxycitronellai and indol; phenyl acetaldehyde and indol; 4-(4-hydroxy-4-methy! pentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate.
More examples of perfume components are, geraniol; geranyl acetate; iinalool;
linalyl acetate; tetrahydrolinalool; citroneilol; citronellyl acetate;
dihydromyrcenol;
dihydromyrcenyl acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl acetate; 2-phenylethanol; 2-phenylethyl acetate; bE~nzyl alcohol; benzyl acetate;
benzyi salicylate; benzyl benzoate; styrallyl acetate; dimethyibenzylcarbinol;
trichloromethylphenylcarbinyl methylpfienylcarbinyl acetate; isononyl acetate;
vetiveryi acetate; vetiverol; 2-methyl-3-(p-tert-butyl>henyl)-propanal; 2-methyl-3-(p-isopropyiphenyl)-propanal; 3-(p-tert-butylphenyl)-propanal; 4-(4-methyl-3-pentenyl)-3-cyciohexenecarbaldehyde; 4-acet:oxy-3-pentyltetrahydropyran;
methyl dihydrojasmonate; 2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyciopentanone; n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate; phenylacetaldehyde dimethylac~etal; phenyiacetaldehyde diethylacetal; geranonitriie; citroneilonitrile; cedryl acetal; 3-isocamphylcyclohexanol; cedryi methylether; isolongifolanone; aubepine nitrite;
aubepine; heliotropine; eugenol; vanillin; Biphenyl oxide; hydroxycitronellal ionones; methyl ionones; isomethyi ionomes; irone~s; cis-3-hexenol and esters thereof; indane musk fragrances; tetralin musk fragrances; isochroman musk fragrances; macrocyclic ketones; macroiactone musk fragrances; ethylene brassylate.
The perfumes useful in the present invention compositions are substantially free of halogenated materials and nitromusks.
Suitable solvents, diiuents or carriers for perfumes ingredients mentioned above are for examples, ethanol, isopropanol, diethylen~e glycol. monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, etc. The amount of such solvents, diluents or carriers incorporated in the perfumes is preferably kept to the minimum needed to provide a homogeneous perfume solution.
Perfume can be present at a level of from 0% to 10%, preferably from 0.1 % to 5%, and more preferably from 0.2% to 3%, by weight of the finished composition. Fabric softener compositions of the present invention provide improved fabric perfume deposition.
Chelatinc~Agents The compositions and processes herein can optionally employ one or more copper andlor nickel chelating agents ("chelators"). Such water-soluble chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. The whiteness andlor brightness of fabrics are substantially improved or restored by such chelating agents and the stability of the materials in the compositions are improved. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional cheiating agents include ethylenediaminetetracetates, N-hydroxyethyle~thylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra-aminehexacetates, diethyierietriaminepentaacetates., and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as. chelating agents in the compositions of-the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionaliy-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkin;~.
WO 00102982 PCTlUS99J15678 The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the dike.
Preferred chelating agents include DETMP, DETPA, NTA, EDDS and mixtures thereof.
If utilized, these chelating agents will generally comprise from about 0.1 %
to about 15% by weight of the fabric care compositions (herein. More preferably, if utilized, the chelating agents will comprise from about 0.1 % to, about 3.0%
by weight of such compositions.
Crystal growth inhibitor component The compositions of the present invention can further contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01 % to 5%, more preferably from 0.1 % to 2% by weight of the compositions.
By organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sec#uestrant components.
The organo diphosphonic acid is preferably a C1-C~ diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
Still useful herein as crystal growth inhibitor are the organic monophosphonic acid Organo monophosphonic acid or one of its salts or compfexes is also suitable far use herein as a CGI.
By organo monophosphonic acid it is meant herein an organo monophosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrants.
The organo monophosphonic acid component may be present in its acid form or in the form of one of its salts or complexes with a suitable counter cation.
Preferably any salts/complexes are water soluble, with the alkali metal and alkaline earth metal salts/complexes being especially preferred.
A preferred organo monophosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid commercially available from Bayer under the tradename of Bayhibit.
Enzyme The compositions and processes herein can optionally employ one or more enzymes such as lipases, proteases, cellulase, amylases and peroxidases. A
preferred enzyme for use herein is a cellulase enzyme. Indeed, this type of enzyme will further provide a color care benefit to the; treated fabric.
Cellulases usable herein include both bacterial and fungal types, preferably having a pH
optimum between 5 and 9.5. U.S. 4,435,307 disctoses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and ceilulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~ aind CELLUZYMEC~ (Novo}
are especially useful. Other suitable cellulases are also disclosed in WO
91/17243 to Novo, WO 96/34092, WO 9fil34945 and EP-A-0,739,982. In practical terms for current commercial preparations, typical amounts are up to mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial enzyme preparation. In the particular cases where activity of the enzyme preparation can be defined otherwise such as with cellulases, corresponding activity units are preferred (e.g. CEVU or cellulase Equivalent Viscosity Units).
Far instance, the compositions of the present invention can contain cellulase enzymes at a level equivalent to an activity from 0.5 to 1000 CEVUlgram of composition. Cellulase enzyme preparations used for the purpose of formulating the compositions of this invention typically have an activity comprised between 1,000 and 10,000 CEVUlgram in liquid form, around 1,000 CEVUlgram in solid form.
Clay The compositions of the invention may preferably contain a clay, preferably present at a level of from 0.05% to 40%, more ~prefPrabiy from 0.5% to 30%;
most preferably from 2% to 20% by weight of the composition. For clarity, it is noted that the term clay mineral compound, as used herein, excludes sodium aiuminosilicate zeolite builder compounds, which hovuever, may be included in the compositions of the invention as optional components.
One preferred clay may be a bentonite clay. Highly preferred are smectite clays, as for example disclosed in the US Patents No.s 3,862,058 3,948,790, 3,954,632 and 4,062,647 and European Patents No.s EP-A-299,575 and EP-A-313,146 all in the name of the Procter and Gamble Company.
The term smectite clays herein includes both the clays in which aluminium oxide is present in a silicate lattice and the clays in which magnesium oxide is present in a silicate lattice. Typical smectite clay compounds include the compounds having the general formula AI2(Si205)2(OH)2.nH20 amd the compounds having the general formula Mg3(Si205)2(OH)2.nH20. Smectite clays tend to adopt an expandable three layer structure.
Specific examples of suitable smectite clays includes those selected from the classes of the montmorillonites, hectorites, vol~chonskoites, nontronites, saponites and sauconites, particularly those having an alkali or alkaline earth metal ion within the crystal lattice structure. Sodium or calcium montmorillonite are particularly preferred.
Suitable smectite clays, particularly montmoriilonitEa, are sold by various suppliers including English China Clays, Laviosa, Georgia Kaolin and Colin Stewart Minerals.
Clays for use herein preferably have a particle diimension of from l0nm to 800nm more preferably from 20nm to 500 mm, most preferably from 50nm to 200 mm.
Particles of the clay mineral compound may be included as components of agglomerate particles containing other detergent compounds. Where present as such components, the term "largest particle dimension" of the clay mineral compound refers to the largest dimension of the clay mineral component as such, and not to the agglomerated particle as a whole.
Substitution of small rations, such as protons, sodium ions, potassium ions, magnesium ions and calcium ions, and of certain organic molecules including those having positively charged functional groups can typically take place within the crystal lattice structure of the smectite clays. A clay may be chosen for its ability to preferentially absorb one ration type, such ability being assessed by measurements of relative ion exchange capacity. The smectite clays suitable herein typically have a ration exchange capacity of at least 50 meq/100g. U.S.
Patent No. 3,954,fi32 describes a method for measurement of ration exchange capacity.
The crystal lattice structure of the clay mineral compounds may have, in a preferred execution, a cationic fabric softening agent substituted therein.
Such substituted clays have been termed 'hydrophobic:ally activated' clays. The cationic fabric softening agents are typically present at a weight ratio, cationic fabric softening agent to clay, of from 1:200 to 7:11); preferably from 1:100 to 1:20. Suitable cationic fabric softening agents incfude> the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 27fi and EP-B-0 011 340.
A preferred commercially available "hydrophobicaily activated" clay is a bentonite clay containing approximately 40% by weight of a dimethyi ditallow quaternary ammonium salt sold under the tradenarr~e Claytone EM by English China Clays International.
In a highly preferred embodiment of the invention, the clay is present in an intimate mixture or in a particle with a humectant and a hydrophobic compound, preferably a wax or oil, such as paraffin oil. Preferred humectants are organic compounds, including propylene glycol, ethylene glycol; dimers or trimers of glycol, most preferably glycerol. The particle is preferably an agglomerate.
Alternatively, the particle may be such that the wax or oil and optionally the humeetant form an encapsulate on the clay or alternatively, the clay be a encapsulate for the wax or oil and the humectant. li: may be preferred that the particle comprises an organic salt or silica or silicate.
However, in another embodiment of the invention, the clay is preferably mixed with . one or more surfactants and optionally builders and optionally water, in which case the mixture is preferably subsequently dried: Preferably, such a mixture is further processed in a spray-drying method to obtain a spray dried particle comprising the clay.
It may be preferred that the flocculating agent is also comprised in the particle or granule comprising the clay.
It may also be preferred that the intimate mixture comprises a cheiating agent.
Flocculatingi agent The compositions of the invention may contain .a clay flocculating agent, preferably present at a level of from 0.005% to 10%, more preferably from 0.05% to 5%, most preferably from 0.1 % to 2% by weight of the composition.
The clay flocculating agent functions such as to bring together the particles of clay compound in the wash solution and hence to aid their deposition onto the surface of the fabrics in the wash. This functional requirement is hence different from that of clay dispersant compounds which are commonly added to laundry detergent compositions to aid the removal of clay soils from fabrics and enable their dispersion within the wash solution.
Preferred as clay flocculating agents herein are organic polymeric materials having an average weight of from 100,000 to 10,000,000, preferably from 150,000 to 5,000,000, more preferably from 200,000 to 2,000,000.
Suitable organic polymeric materials comprise homopolymers or copolymers containing monomeric units selected from aikylene oxide, particularly ethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Homopoiymers of, on particular, ethylene oxide, but also acrylamide and acrylic acid are preferred.
European Patents No.s EP-A-299,575 and EP-A-3'13,146 in the name of the Procter and Gamble Company describe preferred organic polymeric clay flocculating agents for use herein.
The weight ratio of clay to the flocculating polymer is preferably from 1000:1 to 1:1, more preferably from 500:1 to 1:1, most preferably from 300:1 to 1:1, or even more preferably from 80:1 to 10:1, or in certain applications even from 60:1 to 20:1.
Inorganic clay flocculating agents are also suitable therein, typical examples of which include lime and alum.
The flocculating agent is preferably present in a detergent base granule such as a detergent agglomerate, extrudate or spray-dried particle, comprising general3y one or more surfactants and builders.
Effervescent Effervescent means may also be optionally used in the compositions of the invention.
Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate, to produce carbon dioxide gas, i.e. C6H8O7 + 3NaHC03 ~ Na3CgH5O7 + 3C02 1' + 3H20 Further examples of acid and carbonate sources and other effervescent systems may be found in : (Pharmaceutical Dosage Forms : Tablets Volume 1 Page 287 to 291 ).
Carbonate salts Suitable alkali andl or earth alkali inorganic carbonate salts herein include carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like amongst which sodium and potassium ca:~bonate are preferred. Suitable bicarbonates to be used herein include any alkali metal salt of bicarbonate like lithium, sodium, potassium and the like, amongst which sodium and potassium bicarbonate are preferred. However, the choice of carbonate or bicarbonate or mixtures thereof may be made depending on the pH desired in the aqueous medium wherein the granules are dissolved. Far example where a relative high pH is desired in the aqueous medium (e.g., above pH 9.5) it may be preferred to use carbonate alone or to use a combination of carbonate and bicarbonate wherein the level of carbonate is higher than the level of bicarbonate. The inorganic alkali and/ or earth alkali carbonate salt of the compositions of the invention comprises preferably a potassium or more preferably a sodium salt of carbonate andl or bicarbonate. Preferably, the carbonate salt comprises sodium carbonate, optionally also a sodium bicarbonate.
The inorganic carbonate salts herein are preferably present at a level of at least 20% by weight of the composition. Preferably they are present at a level of at least 23% or even 25% or even 30% by weight, preferably up to about 60% by weight or more preferably up to 55% or even 50% by weight.
They may be added completely or partially as separate powdered or granular component, as co-granules with other detergent ingredients, for example other salts or surfactants. In solid detergent compositions of the invention, they may also completely or partially be present in detergent granules such as agglomerates or spray dried granules.
In one embodiment of the invention, an effervescence source is present, preferably comprising an organic acid, such as carboxylic acids or aminoacids, and a carbonate. Then it may be preferred that part or all of the carbonate salt herein is premixed with the organic acid, and thus present in an separate granular component.
Preferred effervescent source are selected from compressed particles of citric acid and carbonate optionally with a binder: and particle of carbonate, WO 00102982 PCT/US991156'78 bicarbonate and malic or malefic acid in weight ratios of 4:2:4. The dry add form of citric acid and carbonate are preferably used.
The carbonate may have any particle size. In one embodiment, in particular when the carbonate salt is present in a granule and not as separately added compound, the carbonate salt has preferably a volume median particle size from 5 to 375 microns, whereby preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume, has a particle size of from to 425 microns. More preferably, the carbon dioxide source has a volume median particle size of 10 to 250, whereby preferably at least 60 %, or even at feast 70% or even at least 80% or even at least 90% by volume, has a particle size of from 1 to 375 microns; or even preferably a volume median particle size from 10 to 200 microns, whereby preferably at least 60 %, preferably at least 70% or even at least 80% or even at least 90% by volume, has a particle size of from 1 to 250 microns.
In particular when the carbonate salt is added as separate component, so to say 'dry-added' or admixed to the other detergent ingredients, the carbonate may have any particle size, including the above specified particle sizes, but preferably at least an volume average particle size of 200 microns or even 250 microns or even 300 microns.
It may be preferred that the carbon dioxide source of the required particle size is obtained by grinding a larger particle size materiiai, optionally followed by selecting the material with the required particle size by any suitable method.
Whilst percarbonate salts may be present in the compositions of the invention as a bleaching agent, they are not included in the carbonate salts as defined herein Other preferred optional ingredients include enzymes stabilisers, polymeric soil release agents, rnateriais effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process (i.e., dye transfer inhibiting agents), polymeric dispersing agents, suds suppressers, optical brighteners or other brightening or whitening agents, anti-static agents, other active ingredients, carriers, hydrotropes: processing aids, dyes or pigments, solvents for liquid formulations and solid fillers for bar compositions.
Form of the composition The composition of the invention may take a variety of physical form including liquid, gel, foam in either aqueous or non-aqueous form, granular and tablet forms.
Liquid detergent compositions can contain water and other solvents as carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubiiizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
Granular detergents can be prepared, for example, by spray-drying (final product density 520 gll) or agglomerating (anal product density above 600 g/l) the Base Granule. The remaining dry ingredients can then be admixed in granular or powder form with the Base Granule, for example in a rotary mixing drum, and the liquid ingredients (e.g., nonionic surfactant and perfume) can be sprayed on.
The detergent compositions herein wilt preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis; acids, etc., and are well~known to those skilled in the art.
When in a liquid form, the composition may also be dispensed by a dispensing means such as a spray dispenser, or aerosol dispenser.
S~~ray Dispenser The present invention also relates to such compositions incorporated into a spray dispenser to create an article of manufacture that can facilitate treatment of fabric articles andlor surfaces with said compasiiuons containing the amine reaction product and other ingredients (exannples are cyclodextrins, polysaccharides, polymers, surfactant, perfume, softener} at a level that is effective, yet is not discernible when dried on the surfaces. The spray dispenser comprises manually activated and non-manual powered (operated) spray means and a container containing the treating composition. Typical disclosure of such spray dispenser can be found in WO 96/04940 page 19 line 21 to page 22 line 27. The articles of manufacture preferably are in association with instructions for use to ensure that the consumer applies sufficient ingredient of the composition to provide the desired benefit. Typical compositions to be dispensed from a sprayer contain a level of amine reaction product of 'from about 0.01 % to about 5%, preferably from about 0.05% to about 2%, more preferably from about 0.1 to about 1 %, by weight of the usage composition.
Method of use The composition of the invention are suitable for use in any step of the domestic treatment, that is a pre-treatment composition, as a wash additive, as a composition suitable for use in the laundry and cleaning process. Obviously, multiple application can be made such as treating the fabric with a pre-treatment composition of the invention and thereafter with the composition suitable for use in the laundry process.
Also provided herein is a method for providing a delayed release of an active ketone or aldehyde which comprises the step of contacting the surface to be treated with a compound or composition of the invention, and thereafter contacting the treated surface with a material, preferably an aqueous medium like moisture or any other means susceptible of releasing the perfume from the amine reaction product.
By "surface", it is meant any surface onto which tree compound can deposit.
Typical examples of such material are fabrics, hard surfaces such as dishware, floors, bathrooms, toilet, kitchen and other surfaces in need of a delayed release of a perfume ketone and/or aldehyde such as that with litter like animal litter.
Preferably, the surface is selected from a fabric, a tile, a ceramic; more preferably is a fabric.
By "delayed release" is meant release of the active component (e.g perfume) over a longer period of time than by the use of the active (e.g., perFume) itself.
Abbreviations used in the followina laundr~r and cleanina composition Examples In the laundry and cleaning compositions, the abbreviated component identifications have the following meanings:
In the detergent compositions, the abbreviated component identifications have the following meanings:
LAS : Sodium linear C11_13 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate CxyAS : Sodium C1x - C1y alkyl sulfate C46SAS : Sodium C14 - C16 secondary (2,3) alkyl sulfate CxyEzS : Sodium C1x-C1y alkyl sulfate condensed with z moles of ethylene oxide CxyEz : C1x-C1y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide QAS : R2.N+{CH3)2(C2H40H) ~nrith R2 = C12 - C14 QAS 1 : R2.N+(CHg}2(C2H40H) with R2 = Cg - C11 APA : Cg - C10 amido propyl dimethyl amine Soap : Sodium linear alkyl carboxylate derived from an 80120 mixture of tallow and coconut tatty acids STS : Sodium toluene sulphonate CFAA : C12-C14 (coco} alkyl N-methyl glucamide TFAA : C16-C1g alkyl N-methyl g~iucamide TPKFA : C12-C14 toPPed whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate TSPP : Tetrasodium pyrophosphate Zeolite A : Hydrated sodium aluminosilicate of formula Nal2(A102Si02)12.27Ha0 having a primary particle size in the range from 0.1 to 10 micrometers {weight expressed on an anhydrous basis) NaSKS-6 : Crystalline layered silicatE: of formula 8-Na2Si205 Citric acid : Anhydrous citric acid Borate : Sodium borate Carbonate : Anydrous sodium carbonate with a particle size between 200pm and 9001am Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400ym and 1200Nm Silicate : Amorphous sodium silical;e (Si02:Na20 = 2.0:1) Sulfate : Anhydrous sodium sulfate:
Mg sulfate : Anhydrous magnesium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425pm and 850um MA/AA : Copolymer of 1:4 malleiclacrylic acid, average molecular weight about 70,000 MAIAA ~( 1 ) Copolymer of 4:6 malleic/acryiic acid, average :
molecular weight about 11),000 AA : Sodium polyacrylate polymer of average molecular weight 4,500 CMC : Sodium carboxymethyl cellulose Cellulose ether Methyl cellulose ether with a degree of :
polymerization of 650 available from Shin Etsu Chemicals Protease : Proteolytic enzyme, having 3.3% by weight of active enzyme, sold by NOVO Industries AIS under the tradename Savinase Protease I : Proteolytic enzyme, having 4% by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc.
Alcalase : Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylase : Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120~T
Lipase : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipase {1) : Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipotase Ultra Endolase : Endogtucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A!S
PB4 : Sodium perborate tetrahydrate of nominal formula NaB02.3H20.H202 PB1 : Anhydrous sodium perborate bleach of nominal fom~ula NaB02.H202 Percarbonate : Sodium percarbonate of nominal formula 2Na2C03.3H202 NOBS : Nonanoyioxybenzene suifonate in the form of the sodium salt NAC-OBS : {6-nonamidocaproyl) oxybenzene sulfonate TAED : Tetraacetylethylenediamine DTPA : Diethylene triamine pentaacetic acid DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Tradename bequest 2060 EDDS : Ethytenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.
Photoactivated Sulfonated zinc phthlocyanine encapsulated : in bleach (1) dextrin soluble polymer Photoactivated Sulfonated alumino phthlocyanine encapsulated : in bleach (2) dextrin soluble polymer Brightener 1 Disodiurn 4,4'-bis(2-suiphostyryl)biphenyl :
Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-:
triazin-2-yl)amino) stilbene:-2:2'-disuifonate HEDP : 1,1-hydroxyethane diphos;phonic acid PEGx : Polyethylene glycol, with a molecular weight of x (typically 4,000) PEO : Polyethylene oxide, with an average molecular weight of 50,000 TEPAE : Tetraethyienepentaamine ethoxyiate PVI : Polyvinyl imidosole, witlh an average molecular weight of 20,000 WO 00/02982 PCTlUS99115678 PVP : Polyvinylpyrolidone polymer, with an average molecular weight of 60,00() PVNO . Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,00() PVPVI : Copolymer of polyvinylpyroiidone and vinylimidazole, with an average molecular weight of 20,000 QEA : bis((C2H50)(C2H40)n)(CIH3) -N~-C6H12-N+-(CH3) bis((C2H50)-(C2H40))n, wherein n = from 20 to 30 SRP 1 : Anionically end capped poly esters SRP 2 : Diethoxylated poly (1, 2 propylene terephtaiate) short block polymer PEI : Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Silicone antifoamPolydimethylsiloxane foann controller with : siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1 Opacifier : Water based monostyrene latex mixture, sold by BASF Aktiengeseilschaft under the tradename Lytron 621 Wax : Paraffin wax PA30 : Polyacryfic acid of average molecular weight of between about 4,500 - 8,000.
480N : Random copolymer of 7:3 acrylatelmethacrylate, average molecular weight about 3,500.
Polygellcarbopol: Higfi molecular weight crosslinked polyacrylates.
Metasilicate ; Sodium metasilicate (Si02:Na20 ratio = 1.0).
Nonionic : C13-C15 mixed ethoxyiated~propoxylated fatty alcohol with an average degree of ethoxyiation of 3.8 and an average degree of propoxylation of 4.5.
Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate, sold by Shell Chemical CO.
MnTACN : Manganese 1,4,7-trimethyl-1.4,7-triazacyclononane.
PAAC : Pentaamine acetate cobait(III) salt.
Paraffin : Paraffin oil sold under they tradename Winog 70 by Wintershall.
NaBz : Sodium benzoate.
BzP : Benzoyl Peroxide.
SCS : Sodium cumene sulphonate.
BTA : Benzotriazole.
pH : Measured as a 1 % solution in distilled water at 20°C.
ARP1 : Amine reaction product of 1,4-bis-(3-aminopropyl)-piperazine with a-Damascone as made from Synthesis example I
ARP2 : Amine reaction product of N,N'bis(arninopropyl)1,3-propanediamine with 8-Da~mascone as made from Synthesis example II
ARP3 : Amine reaction product of polyvinylamine MW1200 with a-Damascone as made from Synthesis example III
Clay I : Bentonite clay Clay II : Smectite clay Flocculating agent t : polyethylene oxide of average molecular weight of between 200,000 and 400,000 Flocculating agent II: polyethylene oxide of average molecular weight of between 400,000 and 1,000,000 Flocculating agent III: polymer of acrylamide ancll or acrylic acid of average molecular weight of 200,000 and 400,000 DOBS: Decanoyi oxybenzene suliFonate in the fofm of the sodium salt SRP 3 : Polysaccharide soil release polymer SRP 4 : Nonionicaily end capped poly esters The following are synthesis examples of compounds as defined in the present invention:
I-Synthesis of 1,4-bis-(3-aminopropyil~-piperazine mith a-Damascone In order to substitute both primary amine groups with .a perfume, 2eq of perfume were used for 1eq of amino functional polymer. To an ice cooled stirred solution WO 00/02982 PCT/US99/156'18 of 1 mmol of a-Damascene in 6 mL EtOH and molecular sieves {4A, 20 g), 0.5eq of 1,4-bis-(3-aminoprapyi)-piperazine was added via an addition funnel.
The reaction mixture was stirred under nitrogen atmosphere and protected from light. After the disappearance of the absorption peak from the NMR spectrum of the free perfume raw material (from 3 to 16 hours), tlhe mixture was filtrated and the solvent was removed by vacuum distillation. The yield of (i-aminoketone formation is about 90%.
Simiiar results were obtained where the a-Damasccme was replaced by Tripal, vertocitral, bourgeonal, or. citronellal. In these instances, Schiff bases are formed.
II-Synthesis of N.N'-bis(3-aminolnropyl -1,3-prouanediamine with _8-Damascone To an ice cooled solution of 1 mmol of 8-Damascene in 30 ml_ EtOH and molecular sieves (4A, 5 g), 0.5eq of the N,N'-bis(3-aminopropyl)-1,3-propanediamine was added. The reaction wa:; stirred under nitrogen atmosphere and protected from light. After 1 day, the molecular sieves and the solvent were removed by filtration and vacuum distillation respectively. ~i-Aminoketone were obtained in a 85 to 90% yield.
Similar results were obtained where the 8-Damascene was replaced by Tripal, vertocitral, bourgeonal, or citronellal. In these instances, Schiff bases are formed.
III-Synthesis of Poiyvinyiamine of MW1 Z00 with a..Damascone The following ingredients were mixed together : 0.6g of Sodium sulfate with 0.3g of polyvinylamine MW 1200 in a 10% aqueous solution and 0.3g a-Damascene.
The reaction was completed after 18 days at room temperature in the dark.
Similar results were obtained where the a-Damascene was replaced by Tripal, or citral: In these instances, Schiff-bases are formed.
In the following formulation examples all levels are quoted as % by weight of the composition unless otherwise stated, and incorporation of the amine reaction product so called herein after "ARP" in the fully formulated composition is carried out by dry addition (d), spray on (s), encapsulation in starch (es) as described in GB-1,464,616 or cyclodextrin (ec) or as is in the composition as defined herein before. The term in bracket for the ARP in the formulation examples refers to the means of incorporation. When none is provided, the incorporation is made as it is. The levels given for the ARP, whether processed or not, refer to the level of ARP as is and not to the processed ARP.
Example 1 The following high density granular laundry detergent compositions were prepared in accord with the invention:
A B C D E F G
LAS 8.0 8.0 8.0 2.0 6.0 6.0 5.0 TAS 0.5 - 0.5 1.0 0.1 1.5 C46(S)AS 2.0 2.5 - - _ -C25AS - 7.0 4.5 5.5 2.5 C68AS 2.0 5.0 7.0 - - _ 0.2 C25E5 - - 3.4 10.0 4.6 4.6 2.6 C25E7 3.4 3.4 1.0 - - - -C25E3S - - 2.0 5.0 4.5 0.5 QAS - 0.8 - - - _ -QAS (I) _ _ _ 0.8 0.5 1.0 1.5 Zeolite A 18.1 18.0 14.1 18.1 20:0 18.1 16.2 Citric acid - - 2.5 _ 2.5 1.5 Carbonate 13.0 13.0 27.0 10.0 10.0 13.0 20.6 SKS-6 - - - 10.0 _ 10.0 4.3 Silicate 1.4 1.4 3.0 0.3 0.5 0.3 Citrate - 1.0 - 3.0 - - 1.4 Sulfate 26.1 26.1 26.1 6.0 - - -Mg sulfate 0.3 - - 0.2 I - 0.2 0.03 A B C D E F G
MAIAA 0.3 0.3 0.3 4.0 1.0 1.0 0.6 CMC 0.2 0.2 0.2 0.2 0.4 0.4 0.3 PB4 9.0 9.0 5.0 - - -Percarbonat- - - - 18.0 18.0 a TAED 1.5 0.4 1.5 - 3.9 4.2 3.2 NAC-OBS - 2.0 1.0 - - -DTPMP 0.25 0.25 0.25 0.25 - -' SRP 2 - - - 0.2 0.2 -EDDS - 0.25 0.4 - 0.5 0.5 0.1 TFAA - - - _ _ - 1.1 C FAA - 1.0 - 2. 0 - -HEDP 0.3 0.3 0.3 0.3 0.4 0.4 0.3 QEA - - 0.2 - 0.5 Protease - - 0.26 1.0 - 0.3 I
Protease 0.26 0.26 1.5 1.0 Cellulase 0.3 - - 0.3 0.3 0.3 0.3 Amylase 0:1 0.1 0.1 0.4 0.5 0.5 0.1 Lipase ( 0.3 - . 0.5 0.5 0.5 0.1 1 ) Photoactivat15 15 15 - 20 20 ppm 20 ed bleach ppm ppm ppm ppm ppm (ppm) PVNOIPVP - - - 0.1 _ Brightener 0.09 0.09 0.09 - 0.09 0.09 0.01 Brightener - - - - _ _ 0:09 Perfume 0.3 0.3 0.3 0.4 0.4 0.4 0.4 spray on A B C D E F G
ARP 1 0.08(d}0.1 - - ..~~ 0.1 0.05(ec)-(es) (d}
ARP 2 - 0.08{s)0.1 (ec} 0.1 -(s}
ARP 3 (es) - - - _ _ 0.4 Silicone 0.5 0.5 0.5 '~ 0.3 0.3 0.3 antifoam Clay II 0.5 0,5 0.5 - 0.3 0.3 12.0 Flocculating0.5 0.5 0.5 - 0.3 0.3 0.3 agent Glycerol 0.5 0.5 0.5 - 0.3 0.3 0.6 Wax 0.5 0.5 0.5 0.3 0.3 0.4 Misc/minors to 100%
Density 850 850 850 850 850 85p 850 in g/litre Example 2 The following granular laundry detergent compositions A to F of particular utility under European machine wash conditions were prepared in accord with the invention:
A B C D E F
1~4S 5.5 7.5 5.0 5.0 6.0 7.0~
TAS 1.25 ~ 1.86 - 0.8 0.4 0.3 C24ASIC25AS - 2.24 5.0 5.0 5.0 2.2 C25E3S - 0.76 1.0 1.5 3.0 1.0 C45E7 3.25 - - - - 3.0 TFAA - - 2.0 - - _ C25E5 - 5.5 - - _ _ QAS 0.8 QAS ll - 0.7 1.0 0.5 1.0 0.7 STPP 19.7 - - - _ _ Zeolite A - 19.5 25.0 19.5 20.0 17.0 I ~
A B C D E F
NaSKS-6lcitric - 10.6 - 10.6 - -acid (79:21 }
NaSKS-6 - - 9.0 - 10.0 10.0 Carbonate 6.1 21.4 9.0 10.0 10.0 18.0 Bicarbonate - 2.0 7.0 5.0 - 2.0 Silicate 6.8 - 0.3 0.5 -Citrate - 4.0 4.0 - -Sulfate 39.8 - 5.0 - 12.0 Mg sulfate - - 0.1 0.2 0.2 MAIAA 0.5 1.6 3.0 4.0 1.0 1.0 CMC 0.2 0.4 1.0 1.0 0.4 0.4 PB4 5.0 12.7 - _ _ Percarbonate - - - - 18.0 15.0 TAED 0.5 3.1 - - 5.0 NAC-OBS 1.0 3.5 - - - 2.5 DTPMP 0.25 0.2 0.3 0.4 - 0.2 HEDP 0.3 - 0.3 0.3 0.3 QEA - 1.0 1.0 1.0 -Protease I - - - 0.5 1.2 -Protease 0.2fi 0.85 0.9 1.0 - 0.7 Lipase { 1 ) 0.15 0.15 0.3 0.3 0.3 0.2 Cellulase 0.28 0.28 0.2 0.2 0.3 0.3 Amylase 0.1 0.1 0.4 0.4 0.6 0.2 PVNOIPVPVI - 0.2 0.2 - -PVP 0.9 1.3 - - - 0.9 SRP 1 - - 0.2 0.2 0.2 -Photoactivated 15 27 - - 20 20 bleach (1) in ppm Photoactivated 15 - - - _ _ bleach (2) in apm Brightener 1 0.08 0.19 - - 0.09 0.15 Brightener 2 - 0.04 - - _ -_ Pertume 0.3 0.3 0.4 0.3 0.4 0.3 ARP1 0.1 1.0(ci)- - - 0.1 {es) (d}
WO 00/029$2 PCT/US99/1567$
A B C C) E P .,_ ARP2~ - 0.04(s) 0.08(ec)0.1 (d) 0.1 (es) Silicone antifoam0.5 2.4 0.3 0.5 0.3 2.0 Minorslmisc to 100%
Density in g/litre750 750 750 T50 750 750 Example 3 The following detergent formulations of particular utility under European machine wash conditions were prepared in accord with the invention.
A __ Blown powder LAS 6.0 5.0 11.0 6.0 TAS 2.0 - - 2,0 Zeolite A 24.0 - - 20.0 STPP - 27.0 24.0 -Sulfate 4.0 6.0 13.0 -MAIAA 1.0 4.0 6.0 2.0 Silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.2 0.2 Silicone antifoam 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray on Brightener 0.02 - - 0.02 C45E7 - - - 5.0 C45E2 2.5 2.5 2.0 -C45E3 2.6 2.5 2.0 -Pertume 0.5 0.3 0.5 0.2 Silicone antifoam 0.3 0.3 0.3 -Dry additives QEA ( - - - 1.0 EDDS I 0.3 - _ Sulfate 2.0 3.0 5.0 10.0 A B C D
Carbonate 6.0 13.0 15.0 14.0 Citric acid 2.5 - - 2.0 QAS f 1 0.5 - - 0. 5 SKS-6 10.0 - - -Percarbonate 18.5 - - -PB4 - 18.0 10.0 21.5 TAED 2.0 2.0 - 2.0 NAC-OBS 3.0 2.0 4.0 -Protease 1.0 1.0 1.0 1.0 Lipase - 0.4 - 0.2 Lipase (1} 0.4 - 0.4 Amylase 0.2 0.2 0.2 0.4 Brightener 1 0.05 - - 0.05 ARP3 0.03 0.1 (es) 1.0 0.1 0.05(ec) Misclminor to 100%
Example 4 The following granular detergent formulations were prepared in accord with the invention.
A B _C D E F
Blown powder LAS 23.0 8.0 7.0 9.0 7.0 7.0 TAS - - - - 1.0 -C45AS 6.0 6.0 5.0 8.0 - -C45AES - 1.0 1.0 1.0 - -C45E35 - - - - 2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MAIAA - 0.5 - - - 2.0 MAIAA ('! ) 7.0 - _ _ _ _ AA - 3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 14.3 11.0 15.0 19.3 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 A B C D E F
Carbonate 15.0 20.0 10.0 20.7 8.0 6.0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA - 0.9 0.5 - - 0.5 Brightener 2 0.3 0.2 0.3 - 0.1 0.3 Spray on C45E7 - 2.0 - - 2.0 2.0 C25E9 3.0 - - - - -C23E9 - - 1.5 2.0 - 2.0 Perfume 0.3 0.3 0.3 2.0 0.3 0.3 ARP2 0.1 0.05(s) - - -{s) Agglomerates C45AS - 5.0 5.0 2.0 - 5.0 BAS - 2.0 2.0 - - 2.0 Zeolite A - 7.5 7.5 8.0 - ?.5 Carbonate - 4.0 4.0 5.0 - 4.0 PEG 4000 - 0.5 0.5 - - 0.5 Misc (water etc) - 2.0 2.0 2.0 - 2.0 Dry additives QAS (I) - _ _ - 1.0 -Citric acid - - - - 2.0 -PB4 - - - - 12.0 1.0 PB1 4.0 1.0 3.0 2.0 - -Percarbonate - - - - 2.0 10.0 Carbonate - 5.3 1.8 - 4.0 4.0 NOBS 4.0 - 6.0 - - 0.6 Methyl cellulose 0.2 - - - - -SKS-6 8.0 - - - - -STS - - 2.0 - 1.0 -Cumene sulfonic acid- 1.0 - - - 2.0 Lipase 0.2 - 0.2 - 0.2 0.4 Cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase 0.2 - 0.1 - 0.2 -Protease 0.5 0.5 0.5 0.3 0.5 0.5 WO 00/029$2 PCTIUS99/15678 A B C D E F
PVPVI - - - - 0.5 0.1 PVP _ - _ _ 0.5 PVNO - 0.5 0.3 - -QEA - - - - 1.0 -SRP1 0.2 0.5 0:3 - 0.2 ARP2 0.1 0.2 0.04(d) 0.02 0.01 0.02(es) (es) Silicone antifoam 0.2 0.4 0.2 0.4 0.1 -Mg sulfate - - 0.2 - -0.2 Misc/minors to 100%
G H I J
Blown powder Clay I or ll 7.0 10.0 6.0 2.0 LAS 16.0 5.0 11.0 6.0 TAS - 5.0 ~- 2.0 Zeolite A - 20.0 ~- 10.0 STPP 24.0 - 14.0 -Sulfate - 2.0 .- -MA/AA - 2.0 1.0 1.0 Silicate 4.0 7.0 3.0 -CMC 1.0 X0.5 0.6 Brightener 1 0.2 0.2 X0.2 0.2 Carbonate 10.0 10.0 20.0 -DTPMP 0.4 0.4 iD.2 Spray on Brightener 1 0.02 - ~- 0.02 C45E7 or E9 - - ;2.0 1.0 C45E3 or E4 - - 2.0 4.0 Perfume 0.5 - 0.5 0.2 Silicone antifoam 0.3 - .. _ Dry additives Flocculating agent 0.3 1.0 1.0 0.5 I or il ~
QEA - _ - 1.0 HEDP/ EDDS 0.3 -Sulfate 2.0 - - -Carbonate 20.0 13.0 15.0 24.0 Citric acid 2.5 - - 2:0 QAS - - Cl.S 0.5 NaSKS-6 3.5 - - 5.0 Percarbonate - - - 9.0 PB4 - - i.0 NOBS - - - 1.3 TAED - - c!.0 1.5 Protease 1.0 1.0 1.0 1.0 Lipase - 0.4 - 0.2 Amylase 0.2 0.2 C1.2 0.4 Brightener 2 0.05 - - 0.05 Perfume 1.0 0:2 C).5 0.3 Speckle 1.2 0.5 ~ 2.0 -ARP1 0.08 1.5 (d) 0.2 0.05 ARP2 3.0(d) 0.6 C).2 0.1 Misc/minor to 100%
Exam,~~le 5 The following nii bleach-containing detergent formulations of particular use in the washing of coloured clothing, according to the present invention were prepared:
A B C
Blown Powder Zeolite A 15.0 15.0 -Sulfate 0.0 5.0 -LAS 3.0 3.0 DTPMP 0.4 0.5 -CMC 0.4 0.4 -MAlAA 4.0 4.0 -Agglomerates C45AS - - 11.0 A B C
LAS 6.0 _ -5.0 TAS 3.0 2.0 -Silicate 4.0 4.0 -Zeolite A 10.0 15.0 13.0 CMC - - 0,5 MAIAA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfume 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2,0 ARP2 0.08(s) - -Dry additives M~~ - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - g,0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 ARP1 0.05 0.08 0.1 (es) Silicone antifoam 5.0 5.0 5.0 Dry additives Sulfate 0.0 9.0 0.0 Misclminors to 100% 100.0 100.0 100.0 Density (g/litre) 700 700 700 Example 6 The following granular detergent formulations were prepared in accord with the invention.
Base granule Zeoiite A 30.0 22.0 24.0 10.0 Sulfate 10.0 5.,0 10.0 7.0 MA/AA 3.0 ~- - -AA - 1..6 2.0 _ MAIAA ( 1 } - 12 .0 - 6.0 LAS 14.0 1CL0 9.0 20.0 C45AS 8.0 7..0 9.0 7.0 C45AES - 1..0 1.0 -Silicate - 1..0 0.5 10.0 Soap - 2..0 -Brightener 1 0.2 0..2 0.2 0.2 Carbonate 6.0 9..0 10.0 10.0 PEG 4000 - 1..0 1.5 -DTPA - 0.,4 - -Spray on C25E9 - .. _ 5,0 C45E7 1.0 1.0 - -C23E9 - 1,0 2.5 -Perfume 0.2 0.3 0.3 -ARP2 0:04(s) -~ - -Dry additives Carbonate 5.0 10.0 18.0 8.0 PVPVI/PVNO 0.5 -~ 0.3 -Protease 1.0 1.0 1.0 0.5 Lipase 0.4 -~ - 0.4 Amylase 0.1 -. - 0.1 Celiuiase 0.1 0.2 0.2 0.1 Noes - a.a - 4.5 PB1 1.0 5.0 1.5 6.0 Sulfate 4.0 5.0 - 5.0 SRPI - 0.4 - _ fi5 ___ A 8 C D
ARP1 0.05 O.CI8 0.1(es) -~
ARP2 0.05 - - 0.02(es) Sud supressor - 0..5 0.5 -Misc/minor to 100%
Example 7 The following granular detergent compositions were prepared in accord with the invention.
A B
T- C
Blown powder _ Zeolite A 20.0 - 15.0 STPP - 20.0 -Sulphate - - 5.0 Carbonate - - 5.0 TAS - - 1.t) LAS 6.0 6.0 6.0 C68AS 2.0 2.0 -Siiicate 3.0 8.0 -MA/AA 4.0 2.0 2.0 CMC O.fi 0.6 i 0.2 Brightener 1 0.2 0.2 0.'I
DTPMP 0.4 0.4 t 0.'I
STS - - 1.0 Spray on C45 E7 5.0 5.0 ~ ~ 4.0 Silicone antifoam 0.3 0.3 I 0.'i Perfume 0.2 0.2 0.3 ARP1 0.1 (s) 0.05(s) 0.08(s) Dry additives 1. () Carbonate 14.0 9.0 ' 10.0 PB1 1.5 2.0 i -PB4 '18.5 13.0 a 13.0 A B C.
TAED 2.0 2.0 2.0 QAS (I) - - 1.0 Photoactivated bleach15 ppm 15 ppm l5ppm SKS-6 - - 3.0 Protease 1.0 1.0 0.2 Lipase 0.2 0.2 0.2 Amylase 0.4 0.4 0.2 Cellulase 0.1 0.1 0.2 Sulfate 10.0 20.0 5.0 Misclminors to 100%
Density {g/litre) 700 700 7CE0 Example 8 The following detergent compositions, according to the present invention were prepared:
A B C
Blown Powder _._ Zeolite A 15.0 15.0 15.0 Sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DTPMP 0.4 0.2 0.4 EDDS - 0.4 0.2 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On A B C
Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 -ARP2 0.02(s) - -Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 -Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 PEO - - 0.2 ARP1 0.1 0.2 0.08(ec) Bentonite clay - - 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 Misclminors to 100% 100.0 1100.0 100.0 Density (g/litre) 850 850 850 D E F G H
Blown Powder STPPI Zeolite 9.0 15.0 15.0 9.0 9.0 A
Flocculating 0.5 0.2 0.9 1.5 -agent II
or III
LAS 7.5 23.0 3.0 7.5 7.5 QAS 2.5 1.5 - - -DTPMP 0.4 0.2 0.4 0.4 0.4 HEDP or EDDS - 0.4 0.2 - -CMC 0.7 0.4 0.4 0.1 0.1 Sodium carbonate _ 20.0 20.0 10.0 5.0 Brightener 0.05 - - 0.05 0.05 Clay I or II - 10.0 - - -STS 0. 5 _ - 0.5 0.
MA/AA 1.5 2.0 2.0 1.5 1.5 Agglomerates Suds suppresser 1.0 1.0 - Z.0 0.5 (silicon) Agglomerate Clay 9.0 - - 4Ø 10.0 Wax 0.5 - - 0.5 1.5 Glycerol 0.5 - - 0.5 0.5 Agglomerate ~S - 5.0 5.0 - _ TAS - 2.0 1.0 - -Silicate 3.0 4.0 - -Zeolite A - 8.0 8.0 -Carbonate - g,0 4,0 _ -Spray On Perfume 0.3 - - 0.3 0.3 C45E7 or E9 2.0 - - 2.0 2.0 C25E3 or E4 2.0 - - 2.0 2.0 Dry additives Citrate or citric2.5 - 2.0 2.5 2.5 acid Clay I or II - 5.0 5.0 -Flocculating agent - - - 0.2 l or II
Bicarbonate - 3.0 - - -Carbonate 15.0 - - 25.0 31.0 TAED 1.0 2.0 5.0 1.0 -Sodium perborate 6.0 7.0 10.0 6.0 or percarbonate SRP1,2,3or4 ~ 0.2 0.1 0.2 0.5 0.3 ~ ~ ~
CMC or nonionic 1.0 1.5 0.5 - -ceflulose ether Protease 0.3 1.0 1.0 0.3 0.3 Lipase - 0.4 0.4 -Amylase 0.2 0.6 0.6 0.2 0.2 Cellulase 0.2 0.6 0.6 0.2 0.2 Silicone antifoam- 5.0 5.0 - -Perfume (starch) 0.2 0.3 1.0 0.2 0.2 Speckle 0.5 0.5 0.1 _ 1.0 -NaSKS-6 (silicate3.5 - -3.5 2R) Photobleach 0.1 - - 0, ~ 0,1 Soap 0.5 2.5 - 0.5 0.5 Sodium sulfate - 3.0 - -ARP1 0.1 1.0(d)0.05 3.0(e:>)0.09 Misc/minors to 100.0 100.0 100.0 100.0 100.
100% 0 Density (g/litre)850 850 850 850 850 Example 9 The following detergent formulations, according to i;he present invention were prepared:
A B C D
LAS 18.0 14.0 :?4.0 20.0 QAS 0.7 1.0 _ 0.7 TFAA - 1.0 - -C23E56.5 - - 1.0 _ C45E7 - 1.0 C45E3S 1.0 2.5 1.0 STPP 32.0 18.0 30.0 22.0 Silicate 9.0 5.0 9.0 8.0 Carbonate 11.0 7.5 10.0 5.0 Bicarbonate - ! 7,5 1 _ _ ~
A B C D
PB1 3.0 1:0 - -PB4 - 1.0 -NOBS 2.0 1.0 - -DTPMP - 1.p _ DTPA 0.5 - 0.2 0.3 SRP 1 0.3 0.2 - 0.1 MAIAA 1. 0 1: 5 2 . 0 - -0. 5 CMC 0.8 0.4 0.4 0.2 PEI - - 0.4 -Sodium sulfate20.0 10.0 x'Ø0 30.0 Mg sulfate 0.2 0.4 0.9 Protease 0.8 1.0 0.5 0:5 Amylase 0.5 0:4 - 0.25 --Lipase 0.2 - X0.1 _ Cellulase 0.15 - - 0.05 Photoactivated30ppm 20ppm - lOpp,r bleach (ppm) ARP3 0.04(s) 0.08(ec) 0..1 (s) 0.04(es) Perfume spray 0.3 0:3 X0.1 0.2 on Brightener 0.05 0.2 0.08 0.1 1l2 Misclminors to 100%
Example 10 The following liquid detergent formulations were prepared in accord with the invention (levels are given as parts per weight}.
A B C D
~S 11.5 8.8 - 3.9 -C25E2.5S - 3.0 18.0 - 16.0 C45E2.25S 11.5 3.0 - 15.7 -C23E9 - 2.7 1.8 2.0 1.0 C23E7 3:2 - _ CFAA - - 5.2 - 3.1 TPKFA 1.6 - 2.0 0.5 2.0 Citric acid (50%} 6.5 1.2 2.5 4.4 2.5 Calcium formate 0.1 0.06 0.1 -Sodium formate 0.5 0.06 0.1 0.05 0.05 Sodium cumene sulfonate4.0 1.0 3.0 1.18 Borate 0.6 - 3.0 2.0 2.9 Sodium hydroxide 5.8 2.0 3.5 3.7 2.7 Ethanol 1.75 1.0 3.6 4.2 2.9 1, 2 propanediol 3.3 2.0 8.0 7.9 5.3 Monoethanolamine 3.0 1.5 1.3 2.5 0.$
TEPAE 1.6 - 1.3 1.2 1.2 Protease 1.0 0.3 1.0 0.5 0.7 Lipase - - 0.1 Cellulase - - 0.1 0.2 0.05 Amylase _ _ _ 0.1 SRP1 0.2 - 0.1 -DTPA - - 0.3 -PVNO - - 0:3 - 0.2 ARP1 0.3 - - 0.1 _ ARP2 - 0.04 - -0.1 ARP3 - - i0.3 -Brightener 1 0.2 0.07 0.1 - _ Silicone antifoam 0.04 0.02 0.1 0.1 0.1 Water/minors Example 11 The following liquid detergent formulations were prepared in accord with the invention (levels are given in parts per weight):
A B C 'D E F G H
LAS 10.0 '! 9.0 - 25.0 - - -3.0 C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0 C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0 C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0 TFAA _ _ ~ 4.5 _ 6.0 8.0 8.0 APA - 1.4 - - 3.0 1.0 2.0 -TPKFA 2.0 - 13.0 _ - 15.0 11.0 11.0 7.0 Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 Dodecenylltetradecenyl12.0 10.0 - - 15.0 - - -succinic acid Rape seed fatty acid4.0 2.0 1.0 - 1.0 - 3.5 -Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 1 3.0 Monoethanolamine - - - 5.0 - - 9.0 _ 9.0 Triethanolamine - - 8.0 _ - _ - -TEPAE 0.5 - 0.5 0.2 - - 0.4 0.3 DTPM P 1.0 1. 0. 1. 2.0 1.2 1. -Protease ~ 0.5 0.5 0.4 0.25 - 0.5 0.3 0.6 Alcalase - - - - 1.5 - - -Lipase - 0.10 - 0.01 - - 0.15 0.15 Amylase 0.25 0:25 0.6 0.5 0.25 0.9 0.6 0.6 Cellulase - - - 0.05 - - 0.15 0.15 Endolase - - - 0.10 - - 0.07 -SRP2 0.3 - 0.3 0.1 - - 0.2 0.1 Boric acid 0.1 0.2 1.0 2.0 1.0 1.5 2.5 2.5 Calcium chloride - 0.02 - 0.01 - - - -Bentonite clay - - - - 4.0 4.0 - -~
Brightener 1 - 0.4 - - 0.1 0.2 0.3 -~
WO 00!02982 PCTIUS99/15678 A B C D E F G H
Sud supressor 0.1 0.3 - 0.1 0.4 - - -Opacifier 0.5 0.4 - 0.3 0.8 0.7 - -ARP1 0.3 - 0.1 - 0.05 - 0.1 0.08 ARP2 - 0.04 - 0.02 - 0.1 0.08 0.1 Water/minors NaOH up to pH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 Example 12 The following liquid detergent compositions were prepared in accord with the invention (levels are given in parts per weight).
A B
~S _ 18. g .. 27.6 C45AS 13.8 5.9 C13E8 3.0 3.1 Oleic acid 3.4 2.5 Citric acid 5.4 5.4 Sodium hydroxide 0.4 3.6 Calcium formate 0,2 0.1 Sodium formate _ 0.5 Ethanol 7.0 _ Monoethanolamine 16.5 ~ 8.0 1,2 propanediol 5.9 5.5 Xylene sulfonic acid - 2.4 TEPAE 1.5 0.8 Protease 1.5 0.6 PEG - 0.7 Brightener 2 0.4 0.1 Perfume spray on 0.5 0.3 ARP1 0.3 -ARP3 - 0.04 WateNminors Example 13 The following is a composition in the form of a tablet, bar, extrudate or granule in accord with the invention A B C D E ~E ~r , Sodium C11-C13 12.0 16.0 23.0 191.0 18.0 20.0 16.0 alkylbenzenesulfonate Sodium C14-C15 alcohol 4 -. - - 4.0 sulfate C,d-C..s alcohol ethoxyfate- - 2.0 - 1.0 1.0 1.0 (3) suifate .-Sodium C14-C15 alcohol2 2 - 1 0 0 ' . . . - - 5.0 , ethoxylate CQ C.r, alkyl dimethyl - - 1.0 0.5 2.0 hydroxy ethyl quaternary ammonium salt Tallow fatty acid _ - - - 1.0 Sodium tripolyphosphate23.0 25.0 14.0 22,0 20.0 10.0 20.0 I
Zeo I ite Sodium carbonate 25.0 22.0 35.0 20.0 28.0 41.0 30.0 Sodium Polyacrylate 0.5 0.5 0.5 _ - - _ O.:i (45%) Sodium - - 1.0 1.CI 1.0 2.0 0.5 poiyacrylatelmaieate polymer Sodium silicate (1:6 3.0 6.0 9.0 8.0~ 9.0 6.0 8.0 ratio NaOISi02)(46%) Sodium sulfate - - - - - 2.0 3.0 Sodium perborate/ 5.0 5.0 10.0 - 3.0 1.0 -percarbonate Poly(ethyleneglycol), 1.5 1.5 1.0 1.0 - - 0.5 MW
w4000 (50%) Sodium carboxy methyl 1.0 1.0 1.0 - 0.5 0.5 0.5 cellulose NOBSI DOBS ~ - 1.0 ~ 1.0 0.7 -WO 0'0/02982 PCT/US99/15678 TAED 1.5 1.0 2.5 - 3.0 0.7 -SRP 1 1.5 1.5 1.0 1.0 - 1.0 -Clay I or I I 5.0 6.0 12.0 7, 0 10.04.0 3.0 Flocculating agent 0.2 0.2 3.0 2.0 0.1 1.0 0.5 I or fll Humectant 0.5 1.0 0.5 1..0 0.5 0.5 -Wax 0.5 0.5 1.0 - - 0.5 0.5 Moisture 7.5 7.5 6.0 7..0 5.0 3.0 5.0 Magnesium sulphate - - _ _ _ 0.5 1.5 Chefant - _ _ _ 0.8 0.6 1.0 Enzymes, including - - - - 2.0 1.5 2.0 amylase, cellulase.
protease and lipase ARP2 0.3 3.0(dj- - - _ _ ARP1 0.08 0.1 3.0(d)1.5(es)0.051.0(d) 0.05 Speckle 2.5 4..1 4.2 4.4 5.6 5.0 5.2 minors, e.g. perfume, 2.0 1.0 1.0 1.0 2.5 1.5 1.0 PVP, PVPVI/PVNO, brightener, photo-bleach.
H 1 _I a Sodium C11-C13 23.0 13.0 20.0 18.0 alkylbenzenesuifonate Sodium C14-C15 alcohol sulfate _ 4.0 - -Clay I or I! 5.0 10.0 14.0 6.0 Flocculating agent I or il 0.2 0.3 0.1 0.9 Wax 0.5 0.5 1.0 -Humectant (glyceroil silica) 0.5 2.0 1.5 -C,~-C,~ alcohol ethoxylate sulfate- _ .0 Sodium C14-C15 alcohol ethoxylate2.5 3.5 -( C~-C,4 alkyl dimethyl hydroxy - - 0.5 ethyl quaternary ammonium salt Tallow fatty acid 0.5 - - _ Tallow alcohol ethoxylate (50) - - 1.3 Sodium tripolyphosphate - 4 - 20.0 1.0 Zeolite A, hydrate (0.1-10 micron26.3 _ 21.3 -size) -Sodium carbonate 24.0 22.0 35.0 27.0 Sodium Polyacrylate (45%) 2.4 - 2.7 -Sodium polyacrylate/maleate polymer- - 1.0 2.5 Sodium silicate (1.6 or 2 or 4.0 7.0 2.0 6.0 2.2 ratio NaO/Si02)(46%) Sodium sulfate - 6.0 2.0 -Sodium perboratel percarbonate 8.0 4.0 - 12.0 Poly(ethyleneglycol), MW 4000 1.7 0.4 1.0 -(50%) Sodium carboxy methyl cellulose 1.0 - - 0.3 Citric acid _ _ 3.0 _ NOBSI DOBS 1.2 - - 1.0 TAED 0.6 1.5 - 3.0 Perfume 0.5 1.0 0.3 0.4 SRP 1 - 1.5 1.0 1.0 Moisture 7.5 3.1 6.1 7.3 Magnesium sulphate - _ _ 1.0 Chelant _ _ _ 0.5 speckle 1.0 0.5 0.2 2.7 Enzymes, including amylase. celiulase.- 1.0 - 1.5 protease and lipase ARP1 0.1 3.0(CI)1.0(es)0.3 minors. e.g. brightener, photo-bleach1.0 1.0 1.0 1.0 Example 14 The following laundry bar detergent compositions weire prepared in accord with the invention (levels are given in parts per weight).
A B C D . E F G H
~S - - 19.0 15.0 21.0 6.75 8.8 C28AS 30.0 13.5 - - - 15.75 11.2 22.5 Sodium laurate2.5 9.0 - - _ _ _ -Zeoiite A 2.0 1.25 - - ~ 1:25 1.25 . 1 .25 Carbonate 20:0 3.0 13.0 8.0 10.0 15.0 15.0 _ 10.0 Calcium 27.5 39.0 35.0 - - 40.0 - 40.0 carbonate A B C D E: F G H
Sulfate 5.0 5.0 3.0 5.0 3.0 - - 5.0 TSPP 5.0 - - - -~ 5.0 2.5 -STPP 5.0 15.0 10.0 - -~ 7.0 8.0 10.0 Bentonite clay- 10.0 - - 5.0 _ _ _ DTPMP - 0.7 0.6 - 0.6' 0.7 0.7 0.7 CMC - 1.0 1.0 1.0 1.0 - - 1.0 Talc - - 10.0 15.0 10.0 - - -Siiicate - - 4.0 5.0 3.0 - - -PVNO 0.02 0.03 - 0.01 - 0.02 - -MA/AA 0.4 1.0 - - 0.2 0.4 0.5 0.4 SRP1 0.3 0.3 0:3 0.3 0.3 0.3 0.3 0.3 Protease - 0.12 - 0.08 O.t)8 - - 0.1 Lipase - 0.1 - 0.1 - - - _ Amylase _ - 0.8 - - - 0.1 -Celluiase - 0.15 - - 0.1i 0.1 - -PEO - 0.2 - 0.2 0.3 _ - 0 3 Perfume 1.0 0.5 0.3 0.2 0.~4 - - 0.4 Mg sulfate - - 3.0 3.0 3.~0 - - -ARP1 0.3 - - 0.04 - 0.5 - -ARP2 - 0.04 - - 0.1 - 0.08 _ ARP3 - - 0.3 - - - - 0.3 Brightener 0.15 0.10 0.15 - - - - 0.1 Photoactivated- 15.0 15.0 15.0 15..0 - - 15.0 bleach (ppm) Example 15 The following detergent additive compositions were prepared according to the present invention A B C
~S - 5.0 5.0 STPP 30.0 - 20.0 Zeolite A _ 35.0 20.0 PB1 ~ 20.0 15.0 -ii;
A B C
TAED 10.0 8.0 _ ARP 1 0.3 - 0.1 ARP2 - 0.04 0.02 Protease - 0.3 0.3 Amylase - 0.06 0.06 Minors, water and rnisceilaneous Up to 100%
Example 16 The following compact high density (0.96Kgll;l dishwashing detergent compositions were prepared according to the present invention A B C D E F G H
STPP - - 54.3 51.4 51.4 - - 50,g Citrate 35.0 17.0 - - - 46.1 40.2 Carbonate - 17.5 14.0 14.0 14.0 - 8.0 32.1 Bicarbonate - - - - - 25.4 - _ Silicate 32.0 14.8 14.8 10.0 10.0 i .0 25.0 3.1 Metasilicate- 2.5 - 9.0 9.0 - - _ PB1 1.9 9.7 7.8 7.8 7.8 - -PB4 8.6 - _ _ _ _ _ _ Percarbonate- - - - - 6.7 11.8 4.8 Nonionic 1.5 2.0 1.5 1.7 1.5 2:6 1.9 5.3 TAED 5.2 2:4 - - - 2.2 - 1.4 HEDP - 1.0 - _ _ _ _ DTPMP - 0,6 _ _ _ - _ -MnTACN - _ _ _ _ _ 0.008 _ PAAC - - 0.008 0.01 0.00T _ _ _ BzP _ _ _ - 1.4 - _ _ Paraffin 0.5 0.5 0.5 0.5 0.5 0.6 - -ARP3 0.1 0.3 0.2 0.05 - - - O.g ARP1 - - - - 0.3 0.03 0.5 -Protease 0.072 0.072 0.029 0.053 0.046 0.026 0.059 0.06 Amylase 0.012 0.012 0.006 0.012 0.013 0.009 0.017 0.03 Lipase - 0.001 - 0.005 - - - _ BTA 0.3 0.3 0.3 0.3 0.3 - 0.3 0.3 I ~;
A B C D E F G H
~
- _ _ _ _ - 4.2 _ MAIAA
480N 3.3 - 6.0 _ _ _ _ _ 0.9 Perfume 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1 Sulphate 7.0 20.0 5.0 2.2 0.8 12.0 4.6 -pH 10.8 11.0 10.8 11.3 11.3 9.6 10.8 10.9 Miscellaneous and Up to '100%
water Exama~le 77 The following granular dishwashing detergent compositions of bulk density 1.02Kg/L were prepared according to the present invention A B C D E F G H
STPP 30.0 30.0 33.0 34.2 29.6 31.1 26.6 17.6 Carbonate 30.5 30.5 31.0 30.0 23.0 39.4 4.2 45.0 Silicate 7.4 7.4 7.5 7.2 13.3 3.4 43.7 12.4 Metasiiicate- - 4.5 5.1 - - - _ Percarbonate- - - - - 4.0 -PB1 4.4 4.2 4.5 4.5 - - - -NADCC - - - - 2.0 - 1.6 1.0 Nonionic 1.2 1.0 0.7 0.8 1.9 0.7 0.6 0.3 TAED 1.0 - - - _ O,g _ _ PAAC - 0.004 0.004 0.004 - - - -BzP - _ - 1.4 - _ _ Paraffin 0.25 0.25 0.25 0.25 - - - -ARP3 0.3 0.1 0.8 0.2(es} - - 0.1 (ec)0.2 (ec) ARP 1 - - - - 0.3 0.1 0.1 (ec)0.2 {ec) Protease 0.036 0.015 0.03 0.028 - 0.03 - -Amyiase 0.003 0.003 0.01 0.006 - 0.01 - -Lipase 0.005 - 0.001 - - - _ _ BTA 0.15 0.15 0.15 0.15 - - - _ Perfume 0.2 0.2 0.2 0.2 0.1 0.2 0.2 -Sulphate 23.4 25.0 22.0 18.5 30.1 19.3 23.1 23.6 pH 10.8 10.8 11.3 11.3 10.7 11.5 12.7 10.9 Miscellaneous Up to 100%
and water ii.
Example 18 The following tablet detergent compositions were prepared according to the present invention by compression of a granular dishwashing detergent composition at a pressure of 13KNIcm2 using a standard 12 head rotary press:
A B C D E F
STPP - 48.8 49.2 38.0 - 46.8 Citrate 26.4 - - = 31.1 -Carbonate - 5.0 14.0 '15.4 14.4 23.0 Silicate 26.4 14.8 15.0 '12.6 17.7 2.4 , ARP1 0.3 - - - 0.06 -ARP2 - 0.04 - - - 0.08 ARP3 - - 0.3 0.1 (ec)-Protease 0.058 0.072 0.041 0.033 0.052 0.013 Amylase 0.01 0.03 0.012 0.007 0.016 0.002 Lipase 0.005 - - - - _ PB 1 1.6 7.7 12.2 110.6 15.7 -PB4 6.9 - - - - 14.4 Nonionic 1.5 2.0 1.5 11.65 0.8 6.3 PAAC - - 0.02 0.009 -MnTACN - - - - 0.007 -TAE D 4.3 2.5 - - 1.3 1.8 HEDP 0.7 - - 0.7 - 0.4 DTPMP 0.65 - - - - _ Paraffin 0.4 0.5 0.5 0.55 - -BTA 0.2 0.3 0.3 ~0.3 -PA30 3.2 - _ _ _ _ MAIAA _ _ _ - 4.5 0.55 Perfume - - 0.05 Cl.05 0.2 0.2 Sulphate 24.0 13.0 2.3 - 10.7 3.4 Weight of tablet25g 25g 20g 30g 18g 20g pH 10.6 10.6 10.7 10.7 10.9 11.2 Miscellaneous water Up to 1100%
and _ g1 Example 19 The following liquid dishwashing detergent compositions of density 1.40Kg/L
were prepared according to the present invention A B C D
STPP 17.5 17.5 17.2 16.0 Carbonate 2.0 - 2.4 -Sificate 5.3 6.1 14.6 15.7 NaOCI 1.15 1.15 1.15 1.25 Polygen/carbopol 1.1 1.0 1.1 1.25 Nonionic - - 0.1 NaBz 0.75 0.75 - -ARP3 0.3 0.5 0.05 0.1 NaOH - 1.9 - 3.5 KON 2.8 3.5 3.0 -pH 11.0 11.7 10.9 11.0 Sulphate, miscellaneousand water up to 00%
Example 20 The following liquid rinse aid compositions were prepared according to the present invention A B C
Nonionic 12.0 - 14.5 Nonipnic blend - 64.0 Citric 3.2 - fi.5 HEDP 0.5 - -PEG - 5.0 _ SCS 4.8 - 7.0 Ethanol 6.0 8.0 -ARP'f 0.3 - 0,1 ARP2 - 0.04 0.01 pH of the liquid 2.0 7.5 I
Miscellaneous and Up to 1100%
water II
Example 21 The following liquid dishwashing compositions were prepared according to the present invention A B C D E
C17ES 28.5 27.~G 19.2 34.1 34.1 Amine oxide 2.6 5.0 2.0 3.0 3.0 C12 glucose amide - - 6,p _ Betaine 0.9 - - 2.0 2.0 Xylene sulfonate 2.0 4.0 - 2.0 -Neodol C11E9 - - 5.0 - -Polyhydroxy fatty acid amide- - - 6.5 6.5 Sodium diethylene penta acetate- - 0.03 - -(40%) TAED - - - 0.06 0.06 Sucrose - - - 1.5 1.5 Ethanol 4.0 5.5 5.5 9.1 9.1 Alkyl diphenyl oxide disulfonate- - - - 2.3 Ca formate - - - 0.5 1.1 Ammonium citrate 0.06 0.1 - - -Na chloride - 1.0 - - -Mg chloride 3.3 - 0.7 - -Ca chloride - - 0.4 - -Na suffate - - 0.06 -Mg sulfate O,Og _ _ _ _ Mg hydroxide - - - 2.2 2.2 Na hydroxide - - - 1.1 1.1 Hydrogen peroxide 200ppm 0.16 0.006 - -ARP3 0.3 - 0.1 - 0.1 ARP'! - 0.3 - 0.1 0.1 Protease 0.017 0.005 .0035 0.003 0.002 Perfume 0.18 0.09 0.09 0.2 0.2 Water and minors Up to 100%
i', Example 22 The following liquid hard surface cleaning compositions were prepared according to the present invention A B C. D E
ARP2 0.04 - 0.08 - 0.01 ARP3 - 0.3 - 0.125 0.1 Amylase 0.01 0.002 0.005 - -Protease 0.05 0.01 0.02 - -Hydrogen peroxide - - - 6.0 6.8 Acetyl triethyl citrate- - - 2.5 -DTPA - - - 0.2 -Butyl hydroxy toluene- - - 0.05 -EDTA* 0.05 0.05 O.E)5 -Citric l Citrate 2.9 2.9 2.9 1.0 -LAS 0.5 0.5 0.5 - -C 12 AS 0.5 0.5 0. 5 - -C 1 OAS - - - - 1.7 C12(E)S 0.5 0.5 0.5 - -C12,13 E6.5 nonionic 7.0 7.0 7.0 - -Neodol23-6.5 - - - 12.0 -Dobanol23-3 - - - - 1.5 Dobanol91-10 - - - - 1.6 C25AE1.8S - _ - 6.0 Na paraffin sulphonate- - - 6.0 Perfume 1.0 1.0 1.0 0.5 0.2 Propanediol - - - 1.5 Ethoxylated tetraethylene- - - 1.0 -pentaimine 2, Butyl octanol - - - - 0.5 Hexyl carbitol** 1.0 1.0 1.0 - -SCS 1.3 1.3 1.3 - -pH adjusted to 7-12 7-12 7-12 4 -Miscellaneous and Up to 100%
water *Na4 ethylenediamine diacetic acid *Diethylene glycol monohexyt ether i i, Example 23 The following spray composition for cleaning of hard surfaces and removing household mildew was prepared according to the present invention ARP2 0.04 Amylase 0.01 Protease 0.01 Na octyl suifate 2.0 Na dodecyi sulfate 4.0 Na hydroxide 0.8 Silicate 0.04 Butyl carbitol* 4.0 Perfume 0.35 Waterlminors up to 100~0 *Diethylene glycol monobutyl ether Example 24 The following lavatory cleansing block compositions were prepared according to the present invention.
A B C
C16-18 fatty alcoho1l50E0 80.0 - -~S - - 80.0 Nonionic - 1.p Oleoamide surfactant - 26:0 -Partially esterified copolymer of vinylmethyl5.(1 - -ether and malefic anhydride, viscosity 0.1-0.5 Polyethylene glycol MW 8000 - 39.0 -Water-soluble K-polyacrylate MW 4000-8000 - 12.0 -Water-soluble Na-copolymer of acryiamide - 19.0 (70%) and acryciic acid (30%) low MW
Na triphosphate 10.0 - -Carbonate - _ g.0 ARP2 0Ø4 - 0.01 ARP3 - 0.25 0.1 A B C
Dye 2.;i 1.0 1.0 Perfume 3.0 - 7.0 KOH J HCL solution pH 6-11 Example 25 The following toilet bowl cleaning composition was prepared according to the present invention.
A B
C14-15 linear alcohol 7E0 2.0 10.0 Citric acid 10.0 5.0 ARP2 0.04 -ARP3 - 0.1 DTPMP - 1.0 Dye 2.0 1.0 Perfume 3.0 3.0 NaOH
pH Ei-11 Water and minors Up to 100%
Claims (18)
1- A laundry and/or cleaning composition comprising a detersive ingredient and a product of reaction between an amino functional polymer comprising at least one primary and/or secondary amine group and a perfume component selected from ketone, aldehyde, and mixtures thereof, characterised in that said amino functional polymer has an Odour Intensity Index of less than that of a 1% solution of methylanthranilate in dipropylene glycol, and the product of reaction has a Dry Surface Odour index of more than 5.
2- A composition according to Claim 1 wherein said amino functional polymer comprises more than one amino groups, preferably more than 10 amino groups.
3- A composition according to Claims 1-2 wherein said amino functional polymer has a molecular weight ranging from 150 to 2.10E6; preferably from 400-50,000; more preferably from 600 to 40,000.
4- A composition according to Claims 1-3, wherein said amino functional polymer is selected from the polyvinylamines, derivatives thereof, and copolymer thereof, alkylene polyamine, polyaminoacid and copolymer thereof, cross-linked polyaminoacids, amino substituted polyvinylalcohol, polyoxyethylene bis amine or bis aminoalkyl, aminoalkyl piperazine and derivatives thereof, N,N'-bis-(3-aminopropyl)-1,3-propanediamine linear or branched, and mixtures thereof.
5- A composition according to Claim 4, wherein said amino functional polymer is selected from polyvinylamines with a MW ranging from 600 to 50K;
amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
polyoxyethylene bis [amine]; polyoxyethylene bis [6-aminohexyl]; N,N'-bis-(3-aminopropyl}-1,3-propanediamine; 1,4-bis-(3-aminopropyl) piperazine, polylysine, cross-linked polylysine, and/or mixtures thereof.
amino substituted polyvinylalcohol with a MW ranging from 400-300,000;
polyoxyethylene bis [amine]; polyoxyethylene bis [6-aminohexyl]; N,N'-bis-(3-aminopropyl}-1,3-propanediamine; 1,4-bis-(3-aminopropyl) piperazine, polylysine, cross-linked polylysine, and/or mixtures thereof.
6- A composition according to any one of Claims 1-5, wherein said product of reaction is preformed before incorporation into the laundry and cleaning composition.
7- A composition according to any one of Claims 1-6, wherein said product of reaction is present in an amount of from 0.0001% to 10%, preferably from 0.001% to 5%, and more preferably from 0.01% to 2%, by weight of the composition.
8- A composition according to Claims 1-7, wherein said perfume is a perfume aldehyde selected from 1-decanal, benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde; cis/trans-3,7-dimethyl-2,6-octadien-1-al;
heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal, traps-2-hexenal, and mixture thereof.
heliotropin; 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal; alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P.T. Bucinal, lyral, cymal, methyl nonyl acetaldehyde, hexanal, traps-2-hexenal, and mixture thereof.
9- A composition according to Claim 1-7, wherein said perfume is a perfume ketone selected from Alpha Damascone, Delta Damascone, Iso Damascone, Carvone, Gamma-Methyl-Ionone, Iso-E-Super, 2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone, Damascenone, methyl dihydrojasmonate, methyl cedrylone, and mixtures thereof.
10- A composition according to claims 1-7 wherein said perfume has an Odor Detection Threshold lower than 1ppm, more preferably lower than 10ppb.
11- A compositions according to Claim 10 wherein said perfume is selected from undecylenic aldehyde, undecalactone gamma, heliotrapin, dodecalactone gamma, p-anisic aldehyde, para hydroxy-phenyl-butanone, cymal, benzyl acetone, ionone alpha, p.t.bucinal, damascenone, ionone beta and methyl-nonyl ketone, and/or mixtures thereof.
12- A composition according to any one of Claims 1-11, wherein the composition further comprises a clay.
13- A method of delivering residual fragrance to a surface which comprises the steps of contacting said surface with a composition as defined in any one of Claims 1-12, and thereafter contacting the treated surface with a material so that the perfume is released.
14- A method according to Claim 13, wherein said material is water.
15- Use of a compound as defined in any one of Claim 1-12, for the manufacture of a laundry and cleaning composition for delivering residual fragrance on a surface on which it is applied.
16- Use according to Claim 15, wherein said surface is a fabric.
17- Use according to Claim 15, wherein said surface is a tile and/or ceramic.
18- A method of providing improved fabric appearance, improved protection against fabric wear and improved color care to a fabric surface, especially after multiwash cycles, which comprises the steps of contacting said surface with a product of reaction between a primary and/or secondary amine compound and a perfume component selected from ketone, aldehyde, and mixtures thereof or composition as defined in any one of Claims 1-11.
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98870155.3 | 1998-07-10 | ||
EP98870155 | 1998-10-28 | ||
EP98870226.2 | 1998-10-28 | ||
EP98870226A EP0971024A1 (en) | 1998-07-10 | 1998-10-28 | Laundry and cleaning compositions |
EP99870025A EP0971026A1 (en) | 1998-07-10 | 1999-02-11 | Laundry and cleaning compositions |
EP99870025.6 | 1999-02-11 | ||
PCT/US1999/015678 WO2000002982A2 (en) | 1998-07-10 | 1999-07-12 | Laundry and cleaning compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2336666A1 true CA2336666A1 (en) | 2000-01-20 |
Family
ID=27239771
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002336666A Abandoned CA2336666A1 (en) | 1998-07-10 | 1999-07-12 | Laundry and cleaning compositions |
Country Status (16)
Country | Link |
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EP (2) | EP0971026A1 (en) |
JP (1) | JP4493849B2 (en) |
KR (1) | KR20010053480A (en) |
CN (1) | CN1321187A (en) |
AT (1) | ATE339494T1 (en) |
AU (1) | AU4870299A (en) |
BR (1) | BR9912033A (en) |
CA (1) | CA2336666A1 (en) |
CZ (1) | CZ200158A3 (en) |
DE (1) | DE69933230T3 (en) |
ES (1) | ES2273504T3 (en) |
HU (1) | HUP0200238A3 (en) |
ID (1) | ID28314A (en) |
MA (1) | MA24922A1 (en) |
TR (1) | TR200100002T2 (en) |
WO (1) | WO2000002982A2 (en) |
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JP6114072B2 (en) * | 2013-03-06 | 2017-04-12 | 花王株式会社 | Liquid detergent composition for automatic washing machine |
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JP6629003B2 (en) * | 2015-08-06 | 2020-01-15 | 花王株式会社 | Liquid dishwashing detergent composition |
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1999
- 1999-02-11 EP EP99870025A patent/EP0971026A1/en not_active Withdrawn
- 1999-07-12 CA CA002336666A patent/CA2336666A1/en not_active Abandoned
- 1999-07-12 JP JP2000559205A patent/JP4493849B2/en not_active Expired - Fee Related
- 1999-07-12 EP EP99932388A patent/EP1123376B2/en not_active Expired - Lifetime
- 1999-07-12 TR TR2001/00002T patent/TR200100002T2/en unknown
- 1999-07-12 KR KR1020017000417A patent/KR20010053480A/en not_active Application Discontinuation
- 1999-07-12 CN CN99808494A patent/CN1321187A/en active Pending
- 1999-07-12 ID IDW20010074A patent/ID28314A/en unknown
- 1999-07-12 AU AU48702/99A patent/AU4870299A/en not_active Abandoned
- 1999-07-12 AT AT99932388T patent/ATE339494T1/en not_active IP Right Cessation
- 1999-07-12 WO PCT/US1999/015678 patent/WO2000002982A2/en active IP Right Grant
- 1999-07-12 DE DE69933230T patent/DE69933230T3/en not_active Expired - Lifetime
- 1999-07-12 CZ CZ200158A patent/CZ200158A3/en unknown
- 1999-07-12 ES ES99932388T patent/ES2273504T3/en not_active Expired - Lifetime
- 1999-07-12 HU HU0200238A patent/HUP0200238A3/en unknown
- 1999-07-12 MA MA25671A patent/MA24922A1/en unknown
- 1999-07-12 BR BR9912033-0A patent/BR9912033A/en not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20220162522A1 (en) * | 2019-03-26 | 2022-05-26 | Conopco, Inc., D/B/A Unilever | Composition |
Also Published As
Publication number | Publication date |
---|---|
HUP0200238A3 (en) | 2004-01-28 |
WO2000002982A2 (en) | 2000-01-20 |
ES2273504T3 (en) | 2007-05-01 |
JP4493849B2 (en) | 2010-06-30 |
JP2002520495A (en) | 2002-07-09 |
EP1123376B2 (en) | 2012-10-17 |
EP1123376A2 (en) | 2001-08-16 |
AU4870299A (en) | 2000-02-01 |
EP0971026A1 (en) | 2000-01-12 |
ID28314A (en) | 2001-05-10 |
DE69933230T2 (en) | 2007-08-30 |
TR200100002T2 (en) | 2002-09-23 |
HUP0200238A2 (en) | 2002-07-29 |
EP1123376B1 (en) | 2006-09-13 |
KR20010053480A (en) | 2001-06-25 |
MA24922A1 (en) | 2000-04-01 |
DE69933230D1 (en) | 2006-10-26 |
ATE339494T1 (en) | 2006-10-15 |
DE69933230T3 (en) | 2013-02-07 |
BR9912033A (en) | 2001-05-22 |
WO2000002982A3 (en) | 2001-06-14 |
CZ200158A3 (en) | 2002-04-17 |
CN1321187A (en) | 2001-11-07 |
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Legal Events
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EEER | Examination request | ||
FZDE | Discontinued |