GB2343456A - Speckle particles and compositions containing the speckle particles - Google Patents
Speckle particles and compositions containing the speckle particles Download PDFInfo
- Publication number
- GB2343456A GB2343456A GB9824225A GB9824225A GB2343456A GB 2343456 A GB2343456 A GB 2343456A GB 9824225 A GB9824225 A GB 9824225A GB 9824225 A GB9824225 A GB 9824225A GB 2343456 A GB2343456 A GB 2343456A
- Authority
- GB
- United Kingdom
- Prior art keywords
- speckle
- acid
- particles
- crystalline
- particle
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 178
- 239000002245 particle Substances 0.000 title claims abstract description 177
- 239000004094 surface-active agent Substances 0.000 claims abstract description 66
- 239000002253 acid Chemical class 0.000 claims abstract description 50
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 238000004140 cleaning Methods 0.000 claims abstract description 23
- 239000002178 crystalline material Substances 0.000 claims abstract description 21
- 239000000049 pigment Substances 0.000 claims abstract description 7
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 6
- 238000004851 dishwashing Methods 0.000 claims abstract description 4
- 238000010412 laundry washing Methods 0.000 claims abstract description 3
- 239000007844 bleaching agent Substances 0.000 claims description 38
- 239000003599 detergent Substances 0.000 claims description 38
- 239000004615 ingredient Substances 0.000 claims description 29
- 102000004190 Enzymes Human genes 0.000 claims description 24
- 108090000790 Enzymes Proteins 0.000 claims description 24
- 150000007513 acids Chemical class 0.000 claims description 22
- 239000003086 colorant Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 9
- 239000012190 activator Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 150000005323 carbonate salts Chemical class 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 238000004040 coloring Methods 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims description 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 239000007916 tablet composition Substances 0.000 claims 1
- -1 organic acid salt Chemical class 0.000 description 84
- 150000001875 compounds Chemical class 0.000 description 56
- 125000000217 alkyl group Chemical group 0.000 description 49
- 125000004432 carbon atom Chemical group C* 0.000 description 44
- 239000000975 dye Substances 0.000 description 38
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 31
- 239000000463 material Substances 0.000 description 31
- 239000002243 precursor Substances 0.000 description 30
- 239000000047 product 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
- 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 24
- 229940088598 enzyme Drugs 0.000 description 23
- 239000011734 sodium Substances 0.000 description 23
- 229910052708 sodium Inorganic materials 0.000 description 22
- 150000004965 peroxy acids Chemical class 0.000 description 20
- 239000002518 antifoaming agent Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 18
- 239000003945 anionic surfactant Substances 0.000 description 16
- 229920001296 polysiloxane Polymers 0.000 description 16
- 239000010457 zeolite Substances 0.000 description 16
- 125000000129 anionic group Chemical group 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 13
- 229910000323 aluminium silicate Inorganic materials 0.000 description 13
- 150000001412 amines Chemical class 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 150000008051 alkyl sulfates Chemical group 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- 239000003352 sequestering agent Substances 0.000 description 12
- 239000008187 granular material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 108090001060 Lipase Proteins 0.000 description 10
- 102000004882 Lipase Human genes 0.000 description 10
- 239000004367 Lipase Substances 0.000 description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 10
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 235000015165 citric acid Nutrition 0.000 description 10
- 229960004106 citric acid Drugs 0.000 description 10
- 150000004665 fatty acids Chemical class 0.000 description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 description 10
- 235000019421 lipase Nutrition 0.000 description 10
- 229920005646 polycarboxylate Polymers 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 10
- 239000011591 potassium Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 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 9
- 108010065511 Amylases Proteins 0.000 description 8
- 102000013142 Amylases Human genes 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 8
- 229920000620 organic polymer Polymers 0.000 description 8
- 239000000344 soap Substances 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- JPZROSNLRWHSQQ-UHFFFAOYSA-N furan-2,5-dione;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1OC(=O)C=C1 JPZROSNLRWHSQQ-UHFFFAOYSA-N 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000001509 sodium citrate Substances 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 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
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 125000002877 alkyl aryl group Chemical group 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 235000019418 amylase Nutrition 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 6
- 239000003093 cationic surfactant Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 230000000873 masking effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 6
- 229960001790 sodium citrate Drugs 0.000 description 6
- 235000011083 sodium citrates Nutrition 0.000 description 6
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 5
- 108091005804 Peptidases Proteins 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000011872 intimate mixture Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 150000004967 organic peroxy acids Chemical class 0.000 description 5
- 239000002304 perfume Substances 0.000 description 5
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- 159000000000 sodium salts Chemical class 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 235000019832 sodium triphosphate Nutrition 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 125000006850 spacer group Chemical group 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 108010059892 Cellulase Proteins 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
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- 229910019142 PO4 Inorganic materials 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
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- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
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- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 230000002366 lipolytic effect Effects 0.000 description 4
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 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 4
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- 239000011347 resin Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical class [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 4
- 230000003381 solubilizing effect Effects 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
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- 108010056079 Subtilisins Proteins 0.000 description 3
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
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- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
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- 238000006384 oligomerization reaction Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
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- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
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- 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 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical class OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- RRCSSMRVSNZOFR-UHFFFAOYSA-N phenyl 3,5,5-trimethylhexanoate;sodium Chemical compound [Na].CC(C)(C)CC(C)CC(=O)OC1=CC=CC=C1 RRCSSMRVSNZOFR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 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
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- NJKRDXUWFBJCDI-UHFFFAOYSA-N propane-1,1,2,3-tetracarboxylic acid Chemical class OC(=O)CC(C(O)=O)C(C(O)=O)C(O)=O NJKRDXUWFBJCDI-UHFFFAOYSA-N 0.000 description 1
- NJEVMKZODGWUQT-UHFFFAOYSA-N propane-1,1,3,3-tetracarboxylic acid Chemical class OC(=O)C(C(O)=O)CC(C(O)=O)C(O)=O NJEVMKZODGWUQT-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019419 proteases Nutrition 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
- 229940051201 quinoline yellow Drugs 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- BZYSAMJFNABQQM-UHFFFAOYSA-M sodium boric acid hydrogen carbonate 2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound C([O-])(O)=O.B(O)(O)O.[Na+].B(O)(O)O.C(CC(O)(C(=O)O)CC(=O)O)(=O)O BZYSAMJFNABQQM-UHFFFAOYSA-M 0.000 description 1
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 description 1
- DAPMZWDGZVFZMK-UHFFFAOYSA-N sodium;2-[2-[4-[4-[2-(2-sulfophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonic acid Chemical group [Na].[Na].OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=C(C=2C=CC(C=CC=3C(=CC=CC=3)S(O)(=O)=O)=CC=2)C=C1 DAPMZWDGZVFZMK-UHFFFAOYSA-N 0.000 description 1
- RPQSWSMNPBZEHT-UHFFFAOYSA-M sodium;2-acetyloxybenzenesulfonate Chemical compound [Na+].CC(=O)OC1=CC=CC=C1S([O-])(=O)=O RPQSWSMNPBZEHT-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- KQHKITXZJDOIOD-UHFFFAOYSA-M sodium;3-sulfobenzoate Chemical compound [Na+].OS(=O)(=O)C1=CC=CC(C([O-])=O)=C1 KQHKITXZJDOIOD-UHFFFAOYSA-M 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
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000012751 sunset yellow FCF Nutrition 0.000 description 1
- 239000004173 sunset yellow FCF Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004026 tertiary sulfonium compounds Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- QQOWHRYOXYEMTL-UHFFFAOYSA-N triazin-4-amine Chemical class N=C1C=CN=NN1 QQOWHRYOXYEMTL-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
- C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- 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
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Cleaning composition speckle particles contain specific crystalline material which is preferably coloured by addition of a dye pigment and/ or a brightener. The speckle particles are used, in particular in laundry and dish washing compositions. The crystalline material may be a hydrated salt, acid, acid salt, crystalline surfactant or saccharide.
Description
Speckle Particles and
Compositions Containing the Speckle Particles
Technical Field
The invention relates to improved speckle particles and compositions comprising the speckle particles, in particular cleaning compositions.
Background to the Invention
In recent years, detergent manufacturers have introduced in their products small amounts of dyed particles or speckles. It has been found that the detergent users associate products having dyed particles with improved cleaning that the consumer acceptance of product comprising coloured particles is normally higher than product not comprising such coloured particles. Furthermore, the speckles can mask decoloration in the product and/or allows the incorporation in the products of small amounts of ingredients which do not have the colour of the bulk of the product by masking this colour difference.
These speckles are often obtained by spraying-on an aqueous solution of a specific dye onto hygroscopic material and addition of these materials to the other ingredients, or directly onto the final detergent base particles and subsequently drying the thus dyed materials or particles. A problem associated with this method is that the hygroscopic material absorbs large amount of water which may result in caking of the product. This is particularly a problem when higher amounts of aqueous dye-solution need to be used, for example, when very diluted dye solutions are to be used, or strongly dyed particles are needed or the dye is absorbed by the material or particles which are to be dyed.
Another problem associated with detergents comprising large amounts of dye per particle can be that the dye can'bleed'in the presence of water. This may be the case when the detergent is made by spraying on large amounts of aqueous dye solutions, or when the detergent comprises large amount of hygroscopic material or of course, when the detergents are introduced to the washing or cleaning liquid. This'bleeding' may cause colour changes of the product and the packing material. Moreover, under certain conditions, the dye or the dye particles which may deposit on the fabrics, can 'bleed'on the fabrics and cause colour changes on the washed fabric.
Also, it has now been found to be essential that the dye in the product is evenly applied at the surface of the particles and throughout the product, to avoid localised high concentrations of dye, which may amount to any of the above problems.
However, despite these problems. it may be desirable to have speckles particles present in the product to provide the required contrast in the product andl or masking of certain ingredients in the product.
The inventors have now found improved speckle particles which have a certain light reflection, or a certain transparency, which can provide a contrast with the other ingredients of the products, or can mask the undesired colour of other ingredients of the product. In particular, they have found that speckle particles comprising crystalline material can provide the required contrasting and or masking. Hereby. the speckle particles are preferably coloured, although in certain applications even the uncoloured crystalline material may provide a contrast or the masking.
Thus, due to the reflection/transparency potential of these speckles, the amount of colorant required to provide the required contrast or masking can be reduced.
Moreover, the inventors have also found that only limited amounts of dye may be needed, because the crystalline material is less porous and/or hygroscopic and thus absorbs less colorant. Thus, the speckle particles of the invention can be coloured more effectively and efficiently.
Thus, an optimum colour appearance of the product can be obtained with a minimum amount of dye, when the speckle materials of the invention are used.
An additional benefit is that less colorant is introduced in the speckle particles and thus in the compositions comprising the particles. Hereby, the risk of bleeding of the colorant is reduced and the problems associated therewith.
Also, since the speckle particles of the invention may even be able to provide the a contrast andl or masking when not coloured, these speckle particle may be useful in certain products in countries where the use of dyes in such products is not allowed.
Summary of the Invention
The invention provides a cleaning composition speckle particle comprising a crystalline material which is coloured with a colorant. The invention also provides a cleaning composition speckle particle comprising a crystalline material selected from the group comprising crystalline hydrated salts, crystalline acids, crystalline acid salts, crystalline surfactants, saccharides, or mixtures thereof.
The colorant comprises preferably a dye, pigment, brightener or mixtures thereof.
The speckle particle is in particular for incorporation in solid laundry or dish washing or hard-surface cleaning compositions.
The invention also relates to a process for making the compositions and the speckle particle and the use thereof.
Detailed Description of the Invention
Speckle Particles
The speckled particles of the invention may be coloured and may have any colour.
When present in cleaning compositions the speckle may preferably be of another colour than the other ingredients or particles of the compositions. When used herein, 'colour'includes any shade of white and black. The words colorant, coloured and colouring are to be interpreted accordingly.
In a preferred embodiment, the speckle particle is preferably coloured with a dye, pigment or brightener, or mixtures thereof as described hereinafter.
The speckle particle of the invention has a specific light reflection and/or light transparency. Thereto, the speckle particle comprises preferably a crystalline hydrated inorganic salt, a crystalline organic acid salt, a crystalline organic salt, a crystalline surfactant, saccharide or mixtures thereof.
Preferably the crystalline material of the speckle particle has preferably at least a transparancey and/or reflection equal to coarse trisodium citrate dihydrate as available from ADM.
Highly preferred crystalline organic salts include carboxylate salts. Also preferred are crystalline polymeric polycarboxylic acids and salts thereof, preferably poly acrylic and/or maleic acid polymers and salts thereof.
Particular preferred is that the crystalline material comprises trisodium citrate dihydrate, most preferably coloured with a dye.
Preferred hydrated crystalline materials herein are hydrated inorganic salts including hydrated sulphate salt; hydrated carbonate salt; hydrated phosphate salt ; hydrated magnesium salt; hydrated carboxylic acids and/or salts thereof. Highly preferred are sodium sulphate deca hydrate or hepta hydrate; sodium carbonate monohydrate, hepta hydrate or decahydrate; sodium tripolyphosphate, ortho phosphate, meta phosphate and/or pyrophosphate with the applicable hydration numbers, in particular mono, di, tri hexa or deca hydrate; magnesium sulphate mono or hepta hydrate, sodium citrate di hydrate or penta hydrate; glucose, maltose, galactose or fructose or mixtures thereof, in particular sugar.
Also useful can be other ingredients commonly employed in detergent compositions which are crystalline materials, such as crystalline silicate, including crystalline layered silicate.
Preferably, the speckle particle comprises at least 20% by weight of the particle of the crystalline hydrated material, preferably at least 50% or even at least 75%, whereby it may be preferred that the particle is substantially free of amorphous material.
The speckle particle may comprise other ingredients. In one embodiment it is preferred that the speckle particle comprises a binder, to bind the crystalline hydrated material and/or the colorant.
Preferred hereby may be that the speckle particle is made by agglomerating the binder and the crystalline hydrated material and/or the colorant.
Any binder material can be used herein. Preferred binders include water, or mixtures of water with other ingredients, such as surfactant pastes. Also useful are liquid or viscous surfactants, polyalkylene glycols, preferably polyethylene glycol, wax and oils.
In one preferred embodiment, the speckle particle a weight average particle size of 400 microns to 2000 microns, preferably from 500 microns to 1400 microns or even from 600 microns to 1180 microns or even 710 microns to 1000 microns.
When the weight average particle size is from 500 to 1400, it may be preferred hereby that at least 70% or even at least 80% or even at least 90% or even substantially all of the particles has a particle size of from 600 microns to 1180 microns. When the weight average particle size is from 600 to 1180, it may be preferred hereby that at least 70% or even at least 80% or even at least 90% or even substantially all of the particles has a particle size of from 710 microns to 1000 microns.
Namely, it has been found that when the speckle particles have an average particle size within these ranges, a smaller amount of speckle particles can be used to obtain the required result. Also, it been found that the use of speckle particles of a specific particle size ensures a more efficient and controlled dyeing of the particles, which enables the effective use of small amounts of dye per particle whilst obtaining a homogeneously dyed particle.
The speckle particles of this particle size may preferably be obtained by binding smaller particles with a binder, for example by agglomeration, as described herein.
They may also be obtained from larger particle size material, for example by grinding this material. Also, the speckle particle of this particle size may alternatively or additionally be obtained by sieving the particles and selecting the required particle size material.
Other methods for controlling the particle size of crystalline material are known to the skilled person and may also be used to obtain the particles of the required size.
The speckle particle may be coloured by any method known in the art. Preferably colorant is mixed with the crystalline material, preferably in the presence of a binder.
Preferably, the speckle particle herein may be coloured with a colorant, preferably a dye and/or a brightener by spraying the colorant into a mixing-container or mix drum, containing the speckle particles and optionally drying the coloured speckle particles, preferably in a fluidised-bed.
The speckle particles of the invention are preferably dyed particles. The dye used for dyeing the particles as used herein can be a dye stuff or an aqueous solution of a dye stuff or an non-aqueous solution of or mixture with a dye stuff, for example using a carrier material such as a nonionic surfactant or other organic binder material. The use of an non-aqueous solution may have as an advantage herein that no subsequent drying step is needed when the solution is applied to the speckle particles.
It may be preferred that the dye is an aqueous solution comprising a dyestuff, at any level to obtain suitable dyeing of the particles. preferably such that levels of dye solution are obtained up to 2% by weight of the speckle particle, or more preferably up to 0.5% by weight, as described above. Optionally, the dye also comprising other ingredients such as organic binder materials.
The dyestuff can be any suitable dyestuff. Specific examples of suitable dyestuffs include E 104-food yellow 13 (quinoline yellow), El 10-food yellow 3 (sunset yellow FCF). E13 1-food blue 5 (patent blue V), Ultra Marine blue (trade name), E133-food blue 2 (brilliant blue FCF), El40-natural green 3 (chlorophyll and chlorphyllins). El41 and Pigment green 7 (chlorinated Cu phthalocyanine).
Preferred dyestuffs may be Monastral Blue BV paste (trade name) and/or Pigmasol
Green (trade name).
The speckle particle preferably comprise such a dyestuff or even at low levels, preferably only up to 2% or more preferably up to 1% or even up to 0.7% and it may be preferred that the dye is present a t a level of below 0.5% or even 0.2% or even 0.1% by weight of the speckle particle.
Brirhtener The speckle particle herein may be coloured with a brightener, preferably certain types of hydrophilic optical brighteners.
The speckle particle preferably comprise such a brightener at levels of up to 20% or more preferably up to 10% or even up to 5% by weight of the speckle particle.
Hydrophilic optical brighteners useful herein include those having the structural formula:
wherein RI is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl ; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethvl-N-methylamino, morphilino, chloro and amino ; and M is a salt-forming cation such as sodium or potassium.
When in the above formula, RI is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis [ (4-anilino-6- (N-2-bis- hydroxyethyl)-s-triazine-2-yl) amino]-2,2'-stilbenedisulfonic acid and disodium salt.
This particular brightener species is commercially marketed under the tradename
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-CBS-X and Tinopal UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent 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, the brightener is 4,4'-bis [ (4-anilino-6- (N-2- hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino] 2, 2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, Rl is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis [ (4-anilino-6-morphilino-s-triazine-2-yl) amino] 2, 2'stilbenedisulfonic acid, sodium salt. This particular brightener species are commercially marketed under the tradename Tinopal-DMS-X and Tinopal AMS-GX by Ciba Geigy Corporation.
Pigment
The speckle particle may also comprise as a colorant a pigment. Any pigement suitable for cleaning compositions may be used herein.
Compositions
The speckle particle is preferably present in cleaning compositions, preferably granular cleaning compositions. The precise level of speckle particles present in the composition depends in particular on the colour of the degree of light reflection or transparency of the speckle particle, the colour of the speckle particle and the other ingredients of the composition, the particle size of the speckled particles and the other ingredients of the composition, and the application of the composition.
The compositions may comprise the speckle particles at a level any level, but preferably from 0.05% to 50%, more preferably from 0.1% to 30%, more preferably from 0.3% to 10% by weight of the composition.
The cleaning compositions of the invention are preferably solid laundry, dishwashing or hard-surface cleaning compositions, preferably in the form of granules, extrudates, flakes or tablets.
The cleaning composition may additionalcomprise any conventional ingredient, not being the coloured speckle particles herein, commo. ily employed in cleaning compositions, preferred ingredeints described herein after.
The speckle particle of the invention is particularly useful in compositions comprising ingredients which do not have the desired product colour, or in compositions comprising hygroscopic ingredients which may absorb moisture and may cause any dye present, to bleed.
The compositions herein thus preferably comprising ingredients such as particles comprising surfactant, enzymes, bleach activators, cellulose derivative or mixtures thereof, which tend to have an undesired colour.
The surfactant containing particles are preferably agglomerates with anionic and/or nonionic surfactants, preferably with LAS and/or ethoxylated alcohol surfactants.
Also preferred are particles containing peroxy acid bleach precursors, such as TAED.
NAC-OBS, and other OBS-variants, or mixtures thereof.
When a composition herein, containing the speckle particles contains other ingredients in particulate form, it may be preferred that these other particles or part thereof, also have the hereinafter specified weight average particle size, so that a homogeneously distribution of the dye throughout the product can be obtained by reduction of segregation of the particles and thus a reduction of the formation of localised high concentrations of dye. This will also amount to a reduction of the chance of colour changes in the products, packaging material and moreover of the fabrics in the washing or cleaning process.
Then, in one embodiment, it may be preferred that composition preferably comprises granules whereof at least 60%, more preferably at least 80% of have an average particle size, by weight, of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns or even 750 to 1000 microns. It may be preferred that the compositions comprises less than 20% or even less than 10% or 5% by weight of particulate components of a particle size of less than 300 microns, or even 450 microns or even 600 microns, and/or less than 20% or even 10% or even 5% by weight of particulate components of a particle size of more than 1600 microns, or even more than 1400 microns or even 1200 microns.
The composition can be made by any method known in the art, including by agglomeration and/or spray-drying, whereby certain ingredients may be admixed or sprayed-on as described herein. It may be preferred that the composition is made by mixing all or part of the granules, including those made by agglomeration or spraydrying and even the speckle particle of the invention, and subsequently adding a binder and agglomerating the mixture and binder to form agglomerated detergent granules, which may be of the required particle size or which may be sieved to obtain particles of the required size.
The compositions are preferably solid detergents which preferably have a density of at least 350g/litre. more preferably at least 500 litre or even 580 g/litre.
It may be preferred that the detergent composition herein comprise one or more anionic surfactants and an aluminosilicate builder, whereby it is preferred that only small amounts of the aluminosilicate builder and the anionic surfactant are in an intimate mixture, i. e. less than 50% or even less than 30% of the total amount of the anionic surfactant and less than 50% or even less than 30% of the total amount of alumnisilicate; it may even be preferred that substantially no anionic surfactant and aluminosilicate builder are in an intimate mixture. Thus, it may be preferred that the composition comprises at least two separate particles which comprise either anionic surfactant or aluminosilicate.'Intimate mixture'means for the purpose of the invention that the two or more ingredients the component are substantially homogeneously divided in the component or particle. Namely, it has been found that the solubility and/or dispensing of the composition is thereby improved.
It may also be preferred that the composition only comprises low levels of aluminosilicate builder, for example less than 10% or even less than 5% by weight of the composition, whereby it is preferred that the composition comprises highly soluble builders, for example sodium citrate or citric acid, carbonate, and/or crystalline layered silicate.
It may also be preferred that the composition comprises as builder system or as part of the builder system, an agglomerate comprising from 0.5% to 80% by weight a crystalline layered silicate, from 10% to 70% by weight of a surfactant, preferably an anionic surfactant and preferably less than 10% by weight of the agglomerate of free moisture, more preferably 30% to 60% by weight a crystalline layered silicate and 20% to 50% by weight of an anionic surfactant.
Effervescence Component
It may be highly preferred that the detergent composition comprises an effervescence component, preferably comprising an acid source and an alkali source capable of reacting together to form a gas upon contact with water, in particular a carbon dioxide gas, formed by reaction of an organic carboxylic acid and a carbonate source.
For the purpose of the invention, the ingredients of the effervescence components may be present in an intimate mixture with one another, preferably in the form of a granule or the may be present in separate particles.
It may be preferred that the effervescence component is a particulate component having an average particle size, by weight, of from 700 microns to 1400 microns, preferably from 750 microns to 1100 microns, preferably comprising an acid source and an alkali source.
It may be preferred that the effervescence component is substantially free of water, preferably such that no water has been intimately mixed with the effervescence component or part thereof. or that no water is present other than the moisture of the raw materials themselves. Typically, the level of water in intimate mixture with the effervescence component is below 5% by weight of the total granule, preferably below 3% and more preferably below 1.5%, preferably obtainable by dry-powder compaction or pressure agglomeration.
These preferred dry effervescent particles result in a very fast carbon dioxide production and therefore in accelerated dispersibility and dissolution rate of the granular composition. The granular compositions of the present invention as described herein, comprising the dry effervescent granules allow dispensing and dissolution in water of the granular compositions in a shorter period of time and at lower total level of effervescent particles/materials and ensure a faster and more effective delivery of detergent ingredients to the wash.
Suitable acids to be used herein include solid organic, mineral or inorganic acids. salts or derivatives thereof or a mixture thereof. It may be preferred that the acids are mono-, bi-or tri-protonic acids. Such acids include mono-or polycarboxylic acids preferably citric acid, adipic acid, glutaric acid, 3 chetoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, malonic acid. Such acids are preferably used in their acidic forms, and it may be preferred that their anhydrous forms are used, or mixtures thereof. Derivatives also include ester of the acids.
The effervescence component or source preferably comprises a carbonate source, including carbonate, bicarbonate and percarbonate salts, in particular bicarbonate and/or carbonate. Suitable carbonates to be used herein include carbonate and hydrogen carbonate of potassium, lithium, sodium, and the like amongst which sodium and potassium carbonate 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.
Bicarbonate may be preferred to carbonate, because it is more-weigh effective, i. e.. at parity weigh bicarbonate is a larger C02"reservoir"than carbonate. However, the choice of carbonate or bicarbonate or mixtures thereof in the dry effervescent granules may be made depending on the pH desired in the aqueous medium wherein the dry effervescent granules are dissolved. For 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, typically in a weight ratio of carbonate to bicarbonate from 0.1 to 10, more preferably from I to 5 and most preferably from 1 to 2.
Such an effervescence granule may also comprise a binder, including surfactants, such as anionic and nonionic surfactants..
The effervescence component is preferably present in the composition according to the present invention at a level of from 0.5% to 60% by weight, preferably from 2% to 50%, more preferably from 5% to 45% and preferably such that the acid component is present at a level of from 0.3% to 40%, more preferably from 1.0% to 35%, or even 2% to 25% or even to 15% by weight of the composition.
Surfactant
The compositions in accord with the invention preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.
A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U. S. P. 3,929,678 issued to Laughlin and
Heuring on December 30,1975. Further examples are given in"Surface Active
Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U. S. P. 4,259,217 issued to Murphy on March 31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
Anionic Surfactant
The compositions in accord with the present invention preferably comprise an additional anionic surfactant. Essentially any anionic surfactants useful for detersive purposes can be comprised in the detergent composition. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate and sulfonate surfactants are preferred.
Highly preferred are surfactants systems comprising a sulfonate and a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxylsulfates, as described herein, preferably combined with a cationic surfactants as described herein.
Other anionic surfactants include the isethionates such as the acyl isethionates, Nacyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-Cl 8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14 diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
Anionic Sulfate Surfactant
Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates. alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the Cs-C 17 acyl-N-(C 1-C4 alkyl) and-N- (CI-C) hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the linear and branched primary C 1 p-C 1g alkyl sulfates. more preferably the C I I-C 15 branched chain alkyl sulfates and the C 12-C 14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 1 o-C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 11-C18. most preferably c11-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5. moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and/or sulfonate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic Sulfate Surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Anionic Carboxvlate Surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
Suitable alkyl ethoxy carboxylates include those with the formula RO (CH2CH20) X CH2C00-M+ wherein R is a C6 to C 1g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRI-CHR2-O)-R3 wherein R is a C6 to C 18 alkyl group, x is from 1 to 25, R I and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl 1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Certain soaps may also be included as suds suppressors.
Alkali Metal Sarcosinate Surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R 1) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or alkenyl group, R I is a C l-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
Alkoxylated Nonionic Surfactant
Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
\onionic Aikoxylated Alcohol Surfactant
The condensation products of aliphatic alcohols with from I to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein.
The alkyl chain of the aliphatic alcohol can either be straight or branched. primary or secondary. and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
Nonionic Polyhvdroxy Fattv Acid Amide Surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR1Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C 1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably C1 alkyl (i. e., methyl); and R2 is a C$- C31 hydrocarbyl, preferably straight-chain Cs-C 19 alkyl or alkenyl, more preferably straight-chain C9-C 17 alkyl or alkenyl, most preferably straight-chain C 11-C 17 alkyl or alkenyl, or mixture thereof ; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic Fattv Acid Amide Surfactant
Suitable fatty acid amide surfactants include those having the formula: R6CON (R7) 2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C 1-C4 alkyl, C I-C4 hydroxyalkyl, and- (C2H40), (H, where x is in the range of from I 3.
Nonionic AlkYlpolysaccharide Surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U. S. Patent 4,565,647, Llenado, issued January 21,1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e. g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Preferred alkylpolyglycosides have the formula: R20 (CnH2nO) t (glycosylx wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.
Amphoteric Surfactant
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
Suitable amine oxides include those compounds having the formula
R3 (OR4) xNO (R5) 2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof ; x is from 0 to 5, preferably from 0 to 3 ; and each R is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C l o-C 18 alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.
A suitable example of an alkyl aphodicarboxylic acid is Miranol (TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Zwitterionic Surfactant
Zwitterionic surfactants can also be incorporated into the detergent compositions in accord with the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
Suitable betaines are those compounds having the formula R (R') 2N+R2COO' wherein R is a C6-C 18 hydrocarbyl group, each R I is typically C I-C3 alkyl, and R2 is a Cl-Cs hydrocarbyl group. Preferred betaines are C12-18 dimethyl-ammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.
Cationic Surfactants
Suitable cationic surfactants to be used in the detergent herein include the quaternary ammonium surfactants. Preferably the quaternary ammonium surfactant is a mono
C6-C 16, preferably C6-C 10 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also the mono-alkoxylated and bis-alkoxylated amine surfactants.
Another suitable group of cationic surfactants which can be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a, preferably water dispersible, compound having surfactant properties comprising at least one ester (i. e.-COO-) linkage and at least one cationically charged group.
Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No. s 4228042,4239660 and 4260529.
In one preferred aspect the ester linkage and cationically charged group are separated from each other in the surfactant molecule by a spacer group consisting of a chain comprising at least three atoms (i. e. of three atoms chain length). preferably from three to eight atoms, more preferably from three to five atoms, most preferably three atoms. The atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in said chain connects only with carbon atoms in the chain. Thus spacer groups having, for example,-O-O- (i. e. peroxide),
N-N-, and-N-O-linkages are excluded, whilst spacer groups having, for example CH2-O-CH2-and-CH2-NH-CH2-linkages are included. In a preferred aspect the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
Cationic mono-alkoxylated amine surfactants
Highly preferred herein are cationic mono-alkoxylated amine surfactant preferably of the general formula I :
wherein RI is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R2 and R3 are methyl groups; R4 is selected from hydrogen (preferred), methyl and ethyl; X~ is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group ; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
Preferably the ApR4 group in formula I has p= I and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the-OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR4 groups are-CH2CH20H,-CH2CH2CH20H,- CH2CH (CH3) OH and-CH (CH3) CH20H, with--CH2CH20H being particularly preferred. Preferred Rl groups are linear alkyl groups. Linear R I groups having from 8 to 14 carbon atoms are preferred.
Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula
wherein R 1 is C 1 p-C 1 g hydrocarbyl and mixtures thereof, especially C 1 o-C l 4 alkyl, preferably C 10 and C 12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH (CH3) CH20] and [CH2CH (CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
The levels of the cationic mono-alkoxylated amine surfactants used in detergent compositions of the invention is preferably from 0.1% to 20%, more preferably from 0.2% to 7%, most preferably from 0. 3% to 3.0% by weight of the composition.
Cationic Bis-alkoxvlated Amine Surfactant
The cationic bis-alkoxylated amine surfactant preferably has the general formula II :
wherein RI is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms ; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X-is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C 1-C4 alkoxy, especially ethoxy, (i. e.,-CH2CH2O-), propoxy, butoxy and mixtures thereof ; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably I to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula
wherein RI is Clo-C18 hydrocarbyl and mixtures thereof, preferably C'C. C alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R I is derived from (coconut) C 12-C 14 alkyl fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula :
wherein R is Cjo-Cjg hydrocarbyl, preferably C 1 ()-C 14 alkyl, independently p is I to about 3 and q is 1 to about 3, R2 is C 1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy (CH2CH20) units (EO) are replace by butoxy (Bu) isopropoxy [CH (CH3) CH20] and [CH2CH (CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or
Pr and/or i-Pr units.
Perhvdrate Bleaches
An preferred additional components of the compositions is a perhydrate bleach, such as metal perborates, metal percarbonates, particularly the sodium salts. Perborate can be mono or tetra hydrated. Sodium percarbonate has the formula corresponding to 2Na2CO3. 3H202, and is available commercially as a crystalline solid.
The perhydrate bleach may be coated, for example with sulphate salts or carbonate salts or silicate or mixtures thereof.
Potassium peroxymonopersulfate, sodium per is another optional inorganic perhydrate salt of use in the detergent compositions herein.
Bleach Activator
The composition preferably comprises a bleach activator, preferably comprising an organic peroxyacid bleach precursor. It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxy acid bleach precursor, as defined herein.
The bleach activator may also comprise a preformed peroxy acid bleach.
The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
Peroxyacid Bleach Precursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as
0
X-C-L where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
0
X-C-OOH
For the purpose of the invention, hydrophobic peroxyacid bleach precursors produce a peroxy acid of the formula above wherein X is a group comprising at least 6 carbon atoms and a hydrophilic peroxyacid bleach precursor produces a peroxyacid bleach of the formula above wherein X is a group comprising 1 to 5 carbon atoms.
Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.
Suitable peroxyacid bleach precursor compounds typically contain one or more N-or
O-acyl groups, which precursors can be selected from a wide range of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871,2143231 and EP-A-0170386.
Leaving Groups
The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e. g., a wash cycle).
However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
Preferred L groups are selected from the group consisting of :
and mixtures thereof, wherein RI is an alkyl, aryl, c, alkaryl group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from I to 8 carbon atoms, R is
H or R, and Y is H or a solubilizing group. Any of Rl, R3 and R4 may be
substituted by essentially any functional group including, for example alkyl,
hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl
ammonium groups.
The preferred solubilizing groups are-S03-M+,-C02-M+,-S04M+,-N+ (R3) 4X and 0 < --N (R3) 3 and most preferably-S03-M and-C02- : VI+ wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
AlkvI Percarboxvlic Acid Bleach Precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.
Preferred alkyl percarboxylic precursor compounds of the imide type include the N , N, N IN I tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred as hydrophilic peroxy acid bleach precursor.
Other preferred alkyl percarboxylic acid precursors include sodium 3, 5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
Amide Substituted Plkvl Peroxyacid Precursors
Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae : R1-C-N-R2-C--L R--N-C-R2-C-L O R5 O or R5 O O wherein RI is an aryl or alkaryl group with from about 1 to about 14 carbon atoms,
R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. RI preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. Rl may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R I and R5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It can be preferred that R I and R5 forms together with the nitrogen and carbon atom a ring structure.
Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido- caproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene-sulfonate, and the highly preferred (6-nonanamidocaproyl) oxy benzene sulfonate, and mixtures thereof as described in EP-A-0170386.
Perbenzoic Acid Precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the
N-benzol substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzol benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Preformed Orzanic PeroxYacid The detergent composition may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1 % to 15% by weight, more preferably from 1% to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae: R1--C--N-R2--C-OOH O R5 O or R1--N-CR2C---OOH R5 O O wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms. and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A 0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono-and diperazelaic acid, mono-and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.
HeM metal ion sequestrant
The compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant or chelant or chelating agent. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from 0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to 7.5% and most preferably from 0.3% to 2% by weight of the compositions or component
Suitable heavy metal ion sequestrants for use hereir include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1- hydroxy disphosphonates and nitrilo trimethylene phosphonates.
Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1, 1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1, 1 hydroxyethane dimethylene phosphonic acid.
Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2hydroxypropylenediamine disuccinic acid or any salts thereof.
Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317, 542 and EP-A-399,133. The iminodiacetic acid-N-2hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The P-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-Nmonoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.
EP-A-476, 257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A 528, 859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-1, 2,4-tricarboxylic acid are alos suitable.
Glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.
Especially preferred are diethylenetriamine pentacetic acid, ethylenediamine N, N'-disuccinic acid (EDDS) and 1, 1 hydroxyethane diphosphonic acid or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
In particular the chelating agents comprising a amino or amine group can be bleach-sensitive and are suitable in the compositions of the invention.
Another highly preferred ingredient useful in the compositions herein is one or more additional enzymes.
Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3, 533, 139.
Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries
A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename
Termamyl, Duramyl and BAN by Novo Industries AIS. Highly preferred amylase enzymes maybe those described in PCT/US 9703635, and in W095/26397 and W096/23873.
Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % tu 2% active enzyme by weight of the composition.
Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001% to 2% by weight, preferably 0.001 % to 1% by weight, most preferably from 0. 001 % to 0.5% by weight of the compositions.
The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginos and expressing the gene in Aspergillus oryza, as host, as described in
European Patent Application, EP-A-0258 068, which is commercially available from
Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U. S. Patent 4,810,414, Huge-Jensen et al, issued March 7,1989.
Optical Bri, rhtener The compositions herein also preferably contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners, as mentioned above.
Photo-bleaching azent Photo-bleaching agents are preferred ingredients of the compositions herein.
Preferred photo-bleaching agent herein comprise a compounds having a porphin or porphyrin structure.
Porphin and porphyrin, in the literature, are used as synonyms, but conventionally porphin stands for the simplest porphyrin without any substituents; wherein porphyrin is a sub-class of porphin. The references to porphin in this application will include porphyrin.
The porphin structures preferably comprise a metal element or cation, preferably Ca,
Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al, most preferably Zn.
It can be preferred that the photo-bleaching compound or component is substituted with substituents selected from alkyl groups such as methyl, ethyl, propyl, t-butyl group and aromatic ring systems such as pyridyl, pyridyl-N-oxide, phenyl, naphthyl and anthracyl moieties.
The photo-bleaching compound or component can have solubilizing groups as substituents. Alternatively, or in addition hereto the photo-bleaching agent can comprise a polymeric component capable of solubilizing the photo-bleaching compound, for example PVP, PVNP, PVI or co-polymers thereof or mixtures thereof.
Highly preferred photo-bleaching compounds are compounds having a phthalocyanine structure, which preferably have the metal elements or cations described above.
Metal phthalocyanines and their derivatives have the structure indicated in Figure 1 and/or Figure 2, wherein the atom positions of the phthalocyanine structure are numbered conventionally.
The phthalocyanines can be substituted for example the phthalocyanine structures which are substituted at one or more of the 1-4,6,8-11, 13,15-18,20,22-25,27 atom positions.
Water-Soluble Builder Compound
The compositions in accord with the present invention preferably contain a watersoluble builder compound, typically present in detergent compositions at a level of from 1% to 80% by weight. preferably from 10% to 60% by weight, most preferably from 15% to 40% by weight of the composition.
The detergent compositions of the invention preferably comprise phosphatecontaining builder material. Preferably present at a level of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40.
The phosphate-containing builder material preferably comprises tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.
Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, and mixtures of any of the foregoing.
The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Pols carboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Polycarboxylates or their acids containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1, 1, 3-propane tricarboxylates described in British Patent No. 1, 387, 447. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight of the composition.
Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829,1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1, 1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent
Nos. 1,398,421 and 1,398,422 and in U. S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e. g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.
Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.
Partially Soluble or Insoluble Builder Compound
The compositions in accord with the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions at a level of from 0.5% to 60% by weight, preferably from 5% to 50% by weight, most preferably from 8% to 40% weight of the composition.
Examples of largely water insoluble builders include the sodium aluminosilicates. As mentioned above, it may be preferred in one mbodiment of the inevntion, that only small amounts of alumino silicate builder are present.
Suitable aluminosilicate zeolites have the unit cell formula Naz [(A102) z (SiO2) y]. xH20 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B. Zeolite P, Zeolite X,
Zeolite HS and mixtures thereof. Zeolite A has the formula :
Na 12 [AI02) 12 (sio2) 12] xH2O wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [ (A102) g6 (Si02) i06]-276H20.
Another preferred aluminosilicate zeolite is zeolite MAP builder.
The zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.
Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1. 15 and, more particularly, not greater than 1. 07.
In a preferred aspect the zeolite MAP detergent builder has a particle size, expressed as a d50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5. 0 micrometres.
The d50 value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d50 values are disclosed in EP 384070A.
Organic Polymeric Compound
Organic polymeric compounds are preferred additional components of the compositions herein and are preferably present as components of any particulate components where they may act such as to bind the particulate component together.
By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants. and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein, including quatemised ethoxylated (poly) amine clay-soil removal/anti-redeposition agent in accord with the invention.
Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions.
Examples of organic polymeric compounds include the water soluble organic homoor co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000.
The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5, 000 to 10,000, are also suitable herein.
Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000. more particularly 2000 to 8000 and most preferably about 4000.
Highly preferred polymeric components herein are cotton and non-cotton soil release polymer according to U. S. Patent 4,968,451, Scheibel et al., and U. S. Patent 5,415,807, Gosselink et al., and in particular according to US application no. 60/051517.
Another organic compound, which is a preferred clay dispersant/anti-redeposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula :
wherein X is a nonionic group selected from the group consisting of H, C 1-C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e. g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35 ; for cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42.
Other dispersantsl anti-redeposition agents for use herein are described in EP-B011965 and US 4,659,802 and US 4,664,848.
Suds Suppressing Svstem The detergent compositions of the invention, when formulated for use in machine washing compositions, may comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, most preferably from 0.05% to 3% by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.
By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term"silicone"as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued
September 27,1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali
metal salts such as sodium, potassium, and lithium salts, and ammonium and
alkanolammonium salts.
Other suitable antifoam compounds include, for example, high molecular weight
fatty esters (e. g. fatty acid triglycerides), fatty acid esters of monovalent alcohols,
aliphatic Clg-C40 ketones (e. g. stearone) N-alkylated amino triazines such as tri-to
hexa-alkylmelamines or di-to tetra alkyldiamine chlortriazines formed as products of
cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e. g. sodium, potassium, lithium) phosphates and phosphate esters.
A preferred suds suppressing system comprises: (a) antifoam compound, preferably silicone antifoam compound, most preferably
a silicone antifoam compound comprising in combination
(i) polydimethyl siloxane. at a level of from 50% to 99%,
preferably 75% to 95% by weight of the silicone antifoam compound;
and
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by
weight of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is incorporated at a level of
from 5% to 50%, preferably 10% to 40% by weight; (b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide
to propylene oxide ratio of from 1 : 0.9 to 1: 1.1, at a level of from 0. 5% to
10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol
rake copolymer of this type is DC0544, commercially available from DOW
Coming under the tradename DC0544 ; (c) an inert carrier fluid compound, most preferably comprising a C 16-C 18
ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably
8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A highly preferred particulate suds suppressing system is described in EP-A-0210731
and comprises a silicone antifoam compound and an organic carrier material having a
melting point in the range 50 C to 85 C, wherein the organic carrier material
comprises a monoester of glycerol and a fatty acid having a carbon chain containing
from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate
suds suppressing systems wherein the organic carrier material is a fatty acid or
alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture
thereof, with a melting point of from 45 C to 80 C.
Other highly preferred suds suppressing systems comprise polydimethylsiloxane or
mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and
polycarboxylic polymers, such as copolymers of laic and acrylic acid.
Polymeric Dye Transfer Inhibitinz Agents
The compositions herein may also comprise from 0.01 % to 10 %, preferably from
0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine
N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidonepolymers or combinations thereof, whereby these polymers can
be cross-linked polymers.
Polymeric Soil Release Agent
Polymeric soil release agents, hereinafter"SRA", can optionally be employed in the present compositions. If utilized, SRA's will generally comprise from 0.01 % to 10. 0%, typically from 0.1% to 5%, preferably from 0.2% to 3. 0% by weight, of the compositions.
Preferred SRA's typically have hydrophilic segments to hydrophilize 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, thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the SRA to be more easily cleaned in later washing procedures.
Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium (IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.
Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moities covalently attached to the backbone, for example as described in U. S. 4,968,451, November 6,1990 to J. J.
Scheibel and E. P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure ; and tc) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end-capped 1,2propylene/polyoxyethylene terephthalate polyesters of U. S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transesterification/oligomerization of poly (ethyleneglycol) methyl ether, DMT, PG and poly (ethyleneglycol) ("PEG"). Other examples of SRA's include: the partly-and fully-anionic-end-capped oligomeric esters of U. S. 4,721,580, January 26,1988 to
Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6dioxa-8-hydroxyoctanesulfonate ; the nonionic-capped block polyester oligomeric compounds of U. S. 4,702,857, October 27,1987 to Gosselink, for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG, or a combination of DMT,
EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate ; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U. S. 4,877,896,
October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e. g., PEG 3400.
SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U. S. 3,959,230 to Hays, May 25,1976 and U. S. 3,893,929 to
Basadur, July 8,1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the Cl-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U. S. 4,000,093, December 28,1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2. 3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20 C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo
KK.
Additional classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see U. S. 4,201,824, Violland et al. and U. S. 4,240,918 Lagasse et al.; and (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With the proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified.
See U. S. 4,525,524 Tung et al.. Other classes include: (III) anionic terephthalatebased SRA's of the urethane-linked variety, see U. S. 4,201,824, Violland et al.;
Other Optional Ingredients
Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes and filler salts, with sodium sulfate being a preferred filler salt.
Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. Also, preferably combined with a carbonate salt, minor amounts (e. g., less than about 20% by weight) of neutralizing agents, buffering agents, phase regulants, hydrotropes, enzyme stabilizing agents, polyacids, suds regulants, opacifiers, anti-oxidants, bactericides can be present.
Form of the Compositions
The composition of the invention can be made via a variety of methods, including dry-mixing, agglomerating, compaction, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques.
The compositions herein can take a variety of physical forms including liquid, but preferably solid forms such as tablet, flake, pastille and bar, and preferably granular forms.
The compositions in accord with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.
Example I
The following speckle particle is a preferred speckle particle of the invention. coarse sodium citrate dihydrate ex ADM are mixed with Monastral blue BV paste solution in a mixing drum, by spraying the dye paste solution into the drum containing the sodium citrate particles. The coloured particles are subsequently dried, obtaining speckle particles comprising 1000ppm of dye.
Abbreviations used in the Granular Detergent Composition Examples
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 C I x-C ly alkyl sulfate
C46SAS Sodium C 14-C 16 secondary (2, 3) alkyl sulfate
CxyEzS Sodium C 1 x-C 1 y alkyl sulfate condensed with z moles of
ethylene oxide
CxyEz C I x-C 1 y predominantly linear primary alcohol condensed
with an average of z moles of ethylene oxide
QAS R2. N+ (CH3) 2 (C2H40H) with R2 = C12-C14 QAS 1 R2. N+ (CH3) 2 (C2H40H) with R2 = C8-C 11 APA C8-C 10 amido propyl dimethyl amine
Soap Sodium linear alkyl carboxylate derived from an 80/20
mixture of tallow and coconut fatty acids
STS Sodium toluene sulphonate
CFAA C 12-C 14 (coco) alkyl N-methyl glucamide
TFAA C 16-C 18 alkyl N-methyl glucamide
TPKFA C 12-C 14 topped whole cut fatty acids
STPP Anhydrous sodium tripolyphosphate
TSPP Tetrasodium pyrophosphate
Zeolite A Hydrated sodium aluminosilicate of formula
Nal2 (A102Si02) 12.27H20 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 b-Na2Si205 Citric acid Anhydrous citric acid
Borate Sodium borate
Carbonate Anydrous sodium carbonate with a particle size between
200um and 900um Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution
between 4001lm and 12001lu Silicate Amorphous sodium silicate (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 425Fun and 850gm MA/AA Copolymer of 1: 4 maleic/acrylic acid, average molecular
weight about 70,000
MA/AA (1) Copolymer of 4: 6 maleic/acrylic acid, average molecular
weight about 10,000
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 A/S 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
120T
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 Lipolase
Ultra
Endolase Endoglucanase enzyme, having 1.5% by weight of active
enzyme, sold by NOVO Industries A/S
PB4 Particle containing sodium perborate tetrahydrate of nominal
formula NaB02. 3H2 O, the particles having a weight average
particle size of 950 microns, 85% particles having a particle
size of from 850 microns to 950 microns
PB 1 Particle containing anhydrous sodium perborate bleach of
nominal formula NaB02. H O2, the particles having a weight
average particle size of 800 microns, 85% particles having a
particle size of from 750 microns to 950 microns
Percarbonate : Particle containing sodium percarbonate of nominal formula 2Na2CO3. 3H202, the particles having a weight average
particle size of 850 microns, 95% particles having a particle
size of from 750 microns to 950 microns
NOBS Particle comprising nonanoyloxybenzene sulfonate in the form
of the sodium salt, the particles having a weight average
particle size of 750 microns to 900 microns
NAC-OBS Particle comprising (6-nonamidocaproyl) oxybenzene
sulfonate, the particles having a weight average particle size of
from 825 microns to 875 microns
TAED I Particle containing tetraacetylethylenediamine, the particles
having a weight average particle size of from 700 microns to
1000 microns
TAED II Tetraacetylethylenediamine of a particle size from 150
microns to 600 microns
DTPA Diethylene triamine pentaacetic acid
DTPMP Diethylene triamine penta (methylene phosphonate), marketed
by Monsanto under the Tradename Dequest 2060
Photoactivated: Sulfonated zinc phthlocyanine encapsulated in bleach (1)
dextrin soluble polymer
Photoactivated Sulfonated alumino phthlocyanine encapsulated in
bleach (2) dextrin soluble polymer
Brightener 1 Disodium 4,4'-bis (2-sulphostyryl) biphenyl Brightener 2. Disodium 4,4'-bis (4-anilino-6-morpholino-1. 3.5-triazin-2
yl) amino) stilbene-2 : 2'-disulfonate
EDDS Ethylenediamine-N, N'-disuccinic acid, (S, S) isomer in the
form of its sodium salt.
HEDP 1, 1-hydroxyethane diphosphonic 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 Tetraethylenepentaamine ethoxylate
PVI Polyvinyl imidosole, with an average molecular weight of
20,000
PVP Polyvinylpyrolidone polymer, with an average molecular
weight of 60,000
PVNO Polyvinylpyridine N-oxide polymer, with an average
molecular weight of 50,000
PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole, with
an average molecular weight of 20,000
QEA bis ( (C2H50) (C2H40) n) (CH3)-N±C6H12-N± (CH3) bis ((C2H50)-(C2H4 O)) n, wherein n = from 20 to 30
SRP 1 Anionically end capped poly esters
SRP 2 Diethoxylated poly (1, 2 propylene terephtalate) short block
polymer
PEI Polyethyleneimine with an average molecular weight of 1800
and an average ethoxylation degree of 7 ethyleneoxy residues
per nitrogen
Silicone antifoam Polydimethylsiloxane foam 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 Aktiengesellschaft under the tradename Lytron 621
Wax Paraffin wax
Speckle as made in examplel In the following examples all levels are quoted as % by weight of the composition:
TABLE I
The following compositions are in accordance with the invention.
C F Spray-driedGranules LAS 10.0 10.0 15.0 5.0 5.0 10.0 - - TAS - 1.0 - - - MBAS - - 5.0 5.0 - - C45AS - - 1.0 2.0 2.0 - - C45AE3S - - 1.0 - - QAS 1. 0 1. 0 DTPA, HEDP and/or 0.3 0.3 0.5 0.3 EDDS gSO4 0.5 0.5 0.1 Sodium citrate---3. 05. 0 Sodium carbonate 10.0 7.0 15.0 10.0 Sodium sulphate 5. 0 - - 5.0 3.0 Sodium silicate 1.6R - - - - 2.0 ZeoliteA 16.0 18.0 20.0 20.0 SKS-6. 0. 0 AA or AA 1.0 2. 0 11. 0. 0 PEG4000-2.0-1.0-1.0-- QEA 1.0 - - - 10 - - - Brightener 0.05 0.05 0.05 - 0.05 - - - Siliconeoil 0.01 0.01 0.01 - - 0.01 lomerate AS - - - - 2.0 2.0 IBAS - - - - - - 1.0 C45AS ~ 2. 0
AE. 0 0.5 arbonate - - 4.0 1.0 1.0 1.0 Sodium citrate. 0 FAA Citric acid 4. 0 1. 0 1. 0 EA - - - 2.0 2.0 1.0 SRP 1. 0 1. 0. 2 Zeolite A 15. 0 26. 0 15.0 16. 0 Sodium silicate EG - - - - - - 4.0 Builder A lomerates SKS-6 6.0 - - - 6.0 3.0 - 7.0 10.0 LAS 4.0 5.0 - - 5.0 3.0 - 10.0 12.0 Dry-addparticulate components aleic 8.0 10.0 10. 0 4.0 - 8.0 2.0 2.0 4.0 acid/carbonate/bicarbon te (40 : 20: 40) EA - - - 0.2 0.5 - - ACAOBS 3.0 - - 4.5 - - - 2.5 NOBS 1. 0 3.0 3.0 - - - - - 5. 0 AED I 2.5 - - 1.5 2.5 6. 5 1.5 TAED I 2.5 - - 1.5 2.5 6.5 - 1.5 MBAS - - - 8.0 - - 8.0 - 4.0 LAS (flake) 10.0 10.0 - - - - - 8.0 Sprav-on
rightener 0.2 0. 2 0. 3 0. 1 0. 2 0. 1 0. 6 0. 3 7 - - - - - 0. ~. ~ Perfume 1.0 0.5 1.1 0.8 0.3 0.5 0.3 0.5 Dry-add itrate - - 20.0 4. 0 5.0 15.0 - 5.0 Percarbonate 15. 0 0 6. 0 10. 0 - - 24.09 18.0 5.0 erborate - - - - 6.09 18.0 - - hotobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03 Enzymes (cellulase, 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 amylase, protease, ipase) Carbonate 0. 0 10.0 - - - 5.0 8. 0 10. 0 5. 0 Perfume (encapsulated) - 0.5 0.5 - 0.3 - 0.2 Suds suppressor 1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 Citric acid - - - 6.0 6.0 - - - 5.0 Speckle0.50.32.01.05.00.51.50.81.0 SKS-6 - - - 4.0 - - - 6.0 Fillers up to 100% TABLE II The following compositions are in accordance with the invention.
F Spray-Dried Granules LAS 10. 0 10. 0 16. 0 5. 0 5 0 III AS 1. 0 MBAs - - - 5.0 5.0 - -
C45AS 1. 0 2. 0 2. 0 C45AE3S 1. 0 QAS - - 1.0 1.0 DTPA, HEDP and/or 0.3 0.3 0.3 0.3 EDDS MgSO4 0.5 0.4 0.1 Sodiumcitrate 10. 0 12. 0 17. 0. 0. 0 Sodiumcarbonate 15.0 8.0 15.0 10.0 Sodiumsulphate 5.0 5.0 - - 5.0 3.09 Sodium silicate 1. 6R - - - - 2.0 Zeolite A - - - 2. 0 SKS-6. 0. 0 MAIAA or AA 1. 0. 0 10. 0. 0 PEG4000 - 2.0 - 1.0 - 1.0 QEA 1.0 - - - 1.0 Brightener 0.05 0.05 0.05 - 0.05 Siliconeoil 0.01 0.01 0.01 - - 0.01 Asslomerate LAS - - - - - - 2.0 2.0 MBAS 1. 0 C45AS - - - - - - 2.0 - AE3 - - - - - - - 1.0 0.5 Carbonat . 0 1.0 1.0 1. 0 Sodium citrate. 0 Sodium citrate - - - - - - - - 5.0 CFAA - - - - - - - Citricacid - - - - - 4.0 - 1.0 1.0 QEA - - - - - 2.0 2.0 1.0
SRP - - - - - 1. 0 1.0 0. 2 eolite A 15. 0 6. 0 15. 0 16. 0 Sodium silicate PEG - - - - - - 4.0 - TAED II 3.0 1.5 uilder Aeglomerate KS-6 6.0 5.0 - - 6.0 3.0 - 7.0 10.0 AS 4.0 5.0 - - 5.0 3. 0 10. 0 12.0 Dry-add particulate components aleic acid/8. 0 10.0 4.0 4.0 - 8.0 2.0 2.0 4.0 carbonate/bicarbonate 40 : 20: 40) QEA - - - 0.2 0.5 - - - NACAOBS 3.0 - - 1.5 - - - 5.5 NOBS/LOBS/DOBS - 3.0 3.0 - - - - - 5.0 TAED I 2.5 - - 1.5 2.5 6.5 - 1.5 MBAS---8.0--8.0-4.0 LAS (flake) - - - - - - - 8.0 Spray-on Brightener 0.2 0.2 0.3 0.1 0.2 - - 0.6 AE7 - - - - - 0.5 - 0.7 Perfume - - - 0.8 - 0.5 0.8 0.5 1.0 Dry-add Citrate 4.0 - 3.0 4.0 - 5.0 15.0 - 5.0 Percarbonate 15.0 3.l0 6.0 10.0 - - 12.0 18.0 5.0
Perborate. 0 18.0 hotobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03 Enzymes(cellulase, 1.5 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 amylase, protease, Lipase) Carbonate. 0 8. 0 10. 0. 0 Perfume (encapsulated) 0. 6 0. 5 0. 5 0. 5 0. 2 0. 1 0. 6 Sudssuppressor 1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2 oap 0.5 0.2 0.3 3.0 0.5 - - 0.3 Citricacid - - - 6.0 6.0 - - - 5.0 Speckle 0.5 0.5 5.0 2.0 0.2 2.5 0.5 0.5 1.0 SKS-6. 0. 0 Fillers up to 100%
Claims (14)
- Claims 1. A cleaning composition speckle particle comprising a crystalline material which is coloured with a colorant
- 2. A cleaning composition speckle particle comprising a crystalline material selected from the group comprising crystalline hydrated salts, crystalline acids, crystalline acid salts, crystalline surfactants, saccharides, or mixtures thereof.
- 3. A speckle particle according to claim I or 2 which is coloured with a dye, pigment and/or brightener.
- 4. A speckle particle according to claim 1 or 3 wherein the crystalline material comprises: a hydrated sulphate salt; hydrated carbonate salt; a hydrated phosphate salt; a hydrated magnesium salt; a crystalline carboxylic acid or salt thereof ; crystalline silicate; a crystalline polymeric polycarboxylic acid or salts thereof; a crystalline surfactant; a saccheride, preferably sugar; or mixtures thereof.
- 5. A speckle particle according to any of claims 1, and 3 or 4 wherein the crystalline material comprises sodium citrate dihydrate.
- 6. A speckle particle according to any preceding claim comprising a binder.
- 7. A speckle particle according to any preceding claim having a weight average particle size of 300 microns to 2000 microns, preferably from 500 microns to 1400 microns, more preferably from 600 microns to 1180 microns.
- 8. A process for making coloured cleaning composition speckle particles, comprising a crystalline material, by spraying a colorant into a mixing container, containing the speckle particles and mixing the colorant and the speckle particle, and optionally drying the coloured speckle particles.
- 9. A process according to claim 8 wherein the speckle particle comprises crystalline material and a binder, whereby the speckle particle preferably is in the form of an agglomerate.
- 10. A cleaning composition comprising the speckle particle according to any preceding claim at a level of from 0.05% to 30% by weight.
- 11. A composition according to claim 10 comprising a coloured speckle particle and other ingredients, the composition obtainable by a process comprising the steps of a) colouring the speckle particles with a colorant to obtain dyed speckle particles, preferably by spraying a colorant into a mix drum containing the speckle particles; b) optionally drying the coloured speckle particles obtained in step b); c) mixing of the coloured speckle particles of step a) or b) with the other ingredients of the cleaning composition.
- 12. A composition according to claim 10 or 11, being a solid laundry or dishwashing detergent composition, preferably a granular composition, extruded composition or a tablet composition, preferably comprising a particle comprising surfactant, an enzyme, a bleach activator, a cellulose derivative or mixtures thereof.
- 13. Use in a cleaning composition of a speckle particle comprising a crystalline material, preferably a coloured speckle particle, to provide a contrasting appearance with the other ingredients of the composition.
- 14. Use in a cleaning composition of a speckle particle comprising a crystalline material, preferably a coloured speckle particle, to mask undesired colours of other detergent ingredients.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9824225A GB2343456A (en) | 1998-11-06 | 1998-11-06 | Speckle particles and compositions containing the speckle particles |
AU12389/00A AU1238900A (en) | 1998-11-06 | 1999-11-03 | Speckle particles and compositions containing the speckle particles |
JP2000581147A JP2002529583A (en) | 1998-11-06 | 1999-11-03 | Speckle particles and compositions containing speckle particles |
BR9915124-3A BR9915124A (en) | 1998-11-06 | 1999-11-03 | Dot particles and compositions containing dot particles |
CN 99812788 CN1325438A (en) | 1998-11-06 | 1999-11-03 | Speckle particles and compositions containing the speckle particles |
PCT/US1999/025259 WO2000027980A1 (en) | 1998-11-06 | 1999-11-03 | Speckle particles and compositions containing the speckle particles |
EP99971839A EP1124930A1 (en) | 1998-11-06 | 1999-11-03 | Speckle particles and compositions containing the speckle particles |
CA002348603A CA2348603A1 (en) | 1998-11-06 | 1999-11-03 | Speckle particles and compositions containing the speckle particles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9824225A GB2343456A (en) | 1998-11-06 | 1998-11-06 | Speckle particles and compositions containing the speckle particles |
Publications (2)
Publication Number | Publication Date |
---|---|
GB9824225D0 GB9824225D0 (en) | 1998-12-30 |
GB2343456A true GB2343456A (en) | 2000-05-10 |
Family
ID=10841866
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB9824225A Withdrawn GB2343456A (en) | 1998-11-06 | 1998-11-06 | Speckle particles and compositions containing the speckle particles |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1124930A1 (en) |
JP (1) | JP2002529583A (en) |
CN (1) | CN1325438A (en) |
AU (1) | AU1238900A (en) |
BR (1) | BR9915124A (en) |
CA (1) | CA2348603A1 (en) |
GB (1) | GB2343456A (en) |
WO (1) | WO2000027980A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001085893A1 (en) * | 2000-05-05 | 2001-11-15 | The Procter & Gamble Company | Process for making solid cleaning components |
EP1852496A1 (en) * | 2006-05-03 | 2007-11-07 | The Procter & Gamble Company | Liquid detergent |
ES2308931A1 (en) * | 2007-05-24 | 2008-12-01 | Casares Daza, S.L. | Composition of a detergent tablet for the water of a vehicle windshield wiper (Machine-translation by Google Translate, not legally binding) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19943254A1 (en) | 1999-09-10 | 2001-03-15 | Clariant Gmbh | Bleach-active metal complexes |
DE19960744A1 (en) * | 1999-12-16 | 2001-07-05 | Clariant Gmbh | Granular alkali layer silicate compound |
DE10243329B3 (en) * | 2002-09-18 | 2004-06-03 | Bk Giulini Chemie Gmbh & Co. Ohg | Process for coloring sodium carbonate and its use in detergent and cleaning agent formulations |
EP1586629A1 (en) * | 2004-04-08 | 2005-10-19 | The Procter & Gamble Company | Detergent composition with masked colored ingredients |
ES2346309T3 (en) | 2004-07-22 | 2010-10-14 | THE PROCTER & GAMBLE COMPANY | DETERGENT COMPOSITIONS THAT INCLUDE COLORED PARTICLES. |
CA2573996C (en) * | 2004-08-11 | 2010-09-21 | The Procter & Gamble Company | A highly water-soluble solid laundry detergent composition that forms a clear wash liquor upon dissolution in water |
CN101389742B (en) * | 2006-02-25 | 2013-05-29 | 荷兰联合利华有限公司 | Shading dye granule, its use in a detergent formulation and process to make it |
PL2009086T3 (en) * | 2007-06-26 | 2013-10-31 | Sa Minera Catalano Aragonesa Samca | Procedure for colouring non-adsorbent minerals and the product thus obtained |
US8999912B2 (en) | 2007-07-09 | 2015-04-07 | The Procter & Gamble Company | Detergent compositions |
JP6407682B2 (en) * | 2014-11-27 | 2018-10-17 | 花王株式会社 | Method for producing powder detergent composition for clothing |
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-
1999
- 1999-11-03 CA CA002348603A patent/CA2348603A1/en not_active Abandoned
- 1999-11-03 CN CN 99812788 patent/CN1325438A/en active Pending
- 1999-11-03 EP EP99971839A patent/EP1124930A1/en not_active Withdrawn
- 1999-11-03 BR BR9915124-3A patent/BR9915124A/en not_active IP Right Cessation
- 1999-11-03 WO PCT/US1999/025259 patent/WO2000027980A1/en not_active Application Discontinuation
- 1999-11-03 AU AU12389/00A patent/AU1238900A/en not_active Abandoned
- 1999-11-03 JP JP2000581147A patent/JP2002529583A/en not_active Withdrawn
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GB1281019A (en) * | 1968-07-30 | 1972-07-12 | Philadelphia Quartz Co | Tinted granules |
US4443564A (en) * | 1981-09-30 | 1984-04-17 | Colgate-Palmolive Company | Packaged speckled dentifrice |
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GB2213161A (en) * | 1987-12-30 | 1989-08-09 | Procter & Gamble | Vividly colored laundry or cleaning products |
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WO2001085893A1 (en) * | 2000-05-05 | 2001-11-15 | The Procter & Gamble Company | Process for making solid cleaning components |
EP1852496A1 (en) * | 2006-05-03 | 2007-11-07 | The Procter & Gamble Company | Liquid detergent |
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ES2308931A1 (en) * | 2007-05-24 | 2008-12-01 | Casares Daza, S.L. | Composition of a detergent tablet for the water of a vehicle windshield wiper (Machine-translation by Google Translate, not legally binding) |
Also Published As
Publication number | Publication date |
---|---|
WO2000027980A1 (en) | 2000-05-18 |
AU1238900A (en) | 2000-05-29 |
GB9824225D0 (en) | 1998-12-30 |
CN1325438A (en) | 2001-12-05 |
JP2002529583A (en) | 2002-09-10 |
CA2348603A1 (en) | 2000-05-18 |
BR9915124A (en) | 2001-07-31 |
EP1124930A1 (en) | 2001-08-22 |
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