CA2238482C - Composition for treating stains on laundry items and methods of treatment - Google Patents
Composition for treating stains on laundry items and methods of treatment Download PDFInfo
- Publication number
- CA2238482C CA2238482C CA002238482A CA2238482A CA2238482C CA 2238482 C CA2238482 C CA 2238482C CA 002238482 A CA002238482 A CA 002238482A CA 2238482 A CA2238482 A CA 2238482A CA 2238482 C CA2238482 C CA 2238482C
- Authority
- CA
- Canada
- Prior art keywords
- stain
- spot
- alkyl
- textile fabric
- cleaning composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000012190 activator Substances 0.000 claims abstract description 29
- 239000004744 fabric Substances 0.000 claims abstract description 25
- 239000007844 bleaching agent Substances 0.000 claims abstract description 24
- 239000004753 textile Substances 0.000 claims abstract description 22
- 238000004140 cleaning Methods 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 16
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- -1 acylated citrate ester Chemical class 0.000 claims description 34
- 125000000217 alkyl group Chemical group 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000002250 absorbent Substances 0.000 claims description 18
- 230000002745 absorbent Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000003599 detergent Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 10
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000004530 micro-emulsion Substances 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- ODCMOZLVFHHLMY-UHFFFAOYSA-N 1-(2-hydroxyethoxy)hexan-2-ol Chemical compound CCCCC(O)COCCO ODCMOZLVFHHLMY-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 claims description 3
- 229940051250 hexylene glycol Drugs 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 150000003138 primary alcohols Chemical class 0.000 claims description 3
- QQAHAGNPDBPSJP-UHFFFAOYSA-N 1,1,1,2,2,3,3,3-octachloropropane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl QQAHAGNPDBPSJP-UHFFFAOYSA-N 0.000 claims description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000007046 ethoxylation reaction Methods 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- 239000007764 o/w emulsion Substances 0.000 abstract description 2
- 239000007762 w/o emulsion Substances 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Natural products O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001860 citric acid derivatives Chemical class 0.000 description 6
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 5
- HDDLVZWGOPWKFW-UHFFFAOYSA-N Trimethyl citrate Natural products COC(=O)CC(O)(C(=O)OC)CC(=O)OC HDDLVZWGOPWKFW-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000001069 triethyl citrate Substances 0.000 description 3
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 3
- 235000013769 triethyl citrate Nutrition 0.000 description 3
- XMVBHZBLHNOQON-UHFFFAOYSA-N 2-butyl-1-octanol Chemical compound CCCCCCC(CO)CCCC XMVBHZBLHNOQON-UHFFFAOYSA-N 0.000 description 2
- FAGGUIDTQQXDSJ-UHFFFAOYSA-N 3-benzoylazepan-2-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCNC1=O FAGGUIDTQQXDSJ-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000005690 diesters Chemical group 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000010409 ironing Methods 0.000 description 2
- 235000015067 sauces Nutrition 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 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 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GOKVKLCCWGRQJV-UHFFFAOYSA-N 2-[6-(decanoylamino)hexanoyloxy]benzenesulfonic acid Chemical compound CCCCCCCCCC(=O)NCCCCCC(=O)OC1=CC=CC=C1S(O)(=O)=O GOKVKLCCWGRQJV-UHFFFAOYSA-N 0.000 description 1
- ISBYGXCCBJIBCG-UHFFFAOYSA-N 2-[6-(nonanoylamino)hexanoyloxy]benzenesulfonic acid Chemical compound CCCCCCCCC(=O)NCCCCCC(=O)OC1=CC=CC=C1S(O)(=O)=O ISBYGXCCBJIBCG-UHFFFAOYSA-N 0.000 description 1
- JKZLOWDYIRTRJZ-UHFFFAOYSA-N 2-[6-(octanoylamino)hexanoyloxy]benzenesulfonic acid Chemical compound CCCCCCCC(=O)NCCCCCC(=O)OC1=CC=CC=C1S(O)(=O)=O JKZLOWDYIRTRJZ-UHFFFAOYSA-N 0.000 description 1
- QJEINWXAHGQZHL-UHFFFAOYSA-N 2-aminoethanol;2-[bis(2-hydroxyethyl)amino]ethanol Chemical compound NCCO.OCCN(CCO)CCO QJEINWXAHGQZHL-UHFFFAOYSA-N 0.000 description 1
- JCAYXDKNUSEQRT-UHFFFAOYSA-N 2-aminoethoxyboronic acid Chemical compound NCCOB(O)O JCAYXDKNUSEQRT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OLDXODLIOAKDPY-UHFFFAOYSA-N 3-decanoylpiperidin-2-one Chemical compound CCCCCCCCCC(=O)C1CCCNC1=O OLDXODLIOAKDPY-UHFFFAOYSA-N 0.000 description 1
- WVILLSKUJNGUKA-UHFFFAOYSA-N 3-nonanoylpiperidin-2-one Chemical compound CCCCCCCCC(=O)C1CCCNC1=O WVILLSKUJNGUKA-UHFFFAOYSA-N 0.000 description 1
- YILDPURCUKWQHU-UHFFFAOYSA-N 3-octanoylpiperidin-2-one Chemical compound CCCCCCCC(=O)C1CCCNC1=O YILDPURCUKWQHU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 201000004002 Aromatase excess syndrome Diseases 0.000 description 1
- FHNUZQMQPXBPJV-UHFFFAOYSA-N CC(C)(C)CC(C)CC(=O)C1CCCNC1=O Chemical compound CC(C)(C)CC(C)CC(=O)C1CCCNC1=O FHNUZQMQPXBPJV-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- RKWGIWYCVPQPMF-UHFFFAOYSA-N Chloropropamide Chemical compound CCCNC(=O)NS(=O)(=O)C1=CC=C(Cl)C=C1 RKWGIWYCVPQPMF-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ZUBJEHHGZYTRPH-KTKRTIGZSA-N [(z)-octadec-9-enyl] hydrogen sulfate Chemical compound CCCCCCCC\C=C/CCCCCCCCOS(O)(=O)=O ZUBJEHHGZYTRPH-KTKRTIGZSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004171 alkoxy aryl group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 210000000077 angora Anatomy 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UZABCLFSICXBCM-UHFFFAOYSA-N ethoxy hydrogen sulfate Chemical class CCOOS(O)(=O)=O UZABCLFSICXBCM-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical class CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- ONLRKTIYOMZEJM-UHFFFAOYSA-N n-methylmethanamine oxide Chemical compound C[NH+](C)[O-] ONLRKTIYOMZEJM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- GIPRGFRQMWSHAK-UHFFFAOYSA-M sodium;2-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=CC=C1S([O-])(=O)=O GIPRGFRQMWSHAK-UHFFFAOYSA-M 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L25/00—Domestic cleaning devices not provided for in other groups of this subclass
- A47L25/08—Pads or the like for cleaning clothes
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/37—Mixtures of compounds all of which are anionic
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
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- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
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- 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
- C11D3/43—Solvents
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F43/00—Dry-cleaning apparatus or methods using volatile solvents
- D06F43/002—Spotting apparatus
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
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- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- C11D2111/12—
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- C11D2111/44—
Abstract
The present invention relates to a cleaning composition which is an oil-in-water or water-in-oil emulsion, or a solution comprising non-aqueous hydrophobic solvent; and anionic or nonionic surfactant. The cleaning composition further comprises a bleach activator. The invention also relates to a method for treating a spot or stain on a textile fabric using the cleaning composition.
Description
COMPOSITION FOR TREATING STAINS ON LAUNDRY ITEMS AND
METHODS OF TREATMENT
The present invention relates to compositions for treating stains on laundry items. Laundry items can be treated either before or after a conventional laundering process by application of the composition in the region of the stain so that the stain is at least partially released and removal of the stain is made easier.
Emulsions of solvent-aqueous systems are known to be effective as spot pretreating compositions on both hydrophobic and hydrophilic stains.
GB-A-2 194 547, published on 9th March 1988, discloses TM
mixtures of n-dodecane with both short-chain (Neodol 91-6) and long chain (Neodol 45-1) nonionics. The compositions are in the form of liquid solutions; water-in-oil or oil-in-water microemulsions, or gels. However this application does not disclose compositions which comprise bleach activator material.
METHODS OF TREATMENT
The present invention relates to compositions for treating stains on laundry items. Laundry items can be treated either before or after a conventional laundering process by application of the composition in the region of the stain so that the stain is at least partially released and removal of the stain is made easier.
Emulsions of solvent-aqueous systems are known to be effective as spot pretreating compositions on both hydrophobic and hydrophilic stains.
GB-A-2 194 547, published on 9th March 1988, discloses TM
mixtures of n-dodecane with both short-chain (Neodol 91-6) and long chain (Neodol 45-1) nonionics. The compositions are in the form of liquid solutions; water-in-oil or oil-in-water microemulsions, or gels. However this application does not disclose compositions which comprise bleach activator material.
The present invention relates to a cleaning composition which is an oil-in-water or water-in-oil emulsion, or a solution comprising non-aqueous hydrophobic solvent; and anionic or nonionic surfactant.
It is the objective of the present invention to improve the removal of bleachable stains through the application of the composition of the present invention and the application of a bleaching compound, preferably a peroxide compound.
Summary c>f the Invention The objective of the present invention is achieved by providing a cleaning composition which further comprises a bleach activator so that cleaning performance for bleachable stains is enhanced.
In a preferred embodiment there is provided a microemulsion cleaning composition having a pH greater than 10 which is an oil-in-water or water-in-oil microemulsion, comprising:
(i) from 5o to 250 of a non-aqueous hydrophobic solvent selected from the group consisting of deodorised kerosene, chlorinated hydrocarbons, 1,1,1-trichloroethane, perchloroethylene, methylene chloride, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, 2-butoxy ethanol, butyl diethylene glycol ether ethanol, butoxytriglycol, butylene glycol, hexylene glycol, and 2a propyl propanol; (ii) at least 5% of a first anionic or nonionic surfactant; characterised in that the cleaning composition further comprises (iii) a bleach activator present in an amount in a range of from 0.1% to 10% by weight, wherein said bleach activator is selected from the group consisting of amido-derived bleach activators of the formulae selected from the group consisting of R1N (RS) C (0) RZC (0) L and R1C (0) N (R5) RZC (0) L wherein R1 is an alkyl group containing from 6 to 12 atoms, RZ is an alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is a leaving group; acylated citrate ester bleach activators, benzoxazin bleach activators; acyl lactum bleach activators; and mixtures thereof; and (iv) 5% to 95% water.
The invention also relates to a method for treating a spot or stain on a textile fabric using the cleaning compositions of the invention.
Detailed Description of the Invention t Hydrophobic solvents are an essential feature of the compostions of the present invention. Preferred hydrophobic solvents are defined in terms of Hansen . parameters. A hydrophobic solvent as defined herein is considered to be a solvent having Hansen hydrogen bonding cohesion parameter dH below 18 tJoule/cm3)0.5 - preferred hydrophobic solvents have a Hansen hydrogen bonding cohesion parameter dH below 12 (Joule/cm3)0.5 and a Hansen polar parameter dP below 8 (Joule/cm3)0.5 .
Preferred solvents for use comprise mixtures of hydrocarbons with a flash point no lower than 70°C, an initial boiling point no lower than 130°C, preferably no lower than 145°C and a solidification point not above 20°C
and aliphatic fatty acid esters. More preferred solvents would be alkanes or alkenes with a chain length above C7, and particularly alkanes and alkenes with an average of C8 to C20 atoms. Particularly preferred hydrophobic solvents are deodorised kerosine; solvent naphta; chlorinated hydrocarbons; and terpenes. Even more preferred are paraffins; isoparaffins; naphthenes; aromatics; olefins;
1,1,1-trichloroethane perchloroethylene; methylene chloride; Shellsol SS~ mixture (C8-C11 isoparaffin + 5%
aliphatic C7 ester); D-Limonene; and Glidsafe~ supplied by Glidsol. Solvents are used in the detergent compositions of the present invention preferably at a level of from 3% to 90%, more preferably from 4% to 45%, and most preferably from 5% to 25% by weight of the detergent composition.
Other solvents having a Hansen parameter of dH less than 18 ' (~Toule/cm3)0~5 include glycol ethers, more preferably glycol ethers based upon ethylene oxide, propylene oxide, or mixtures thereof. Particularly preferred are ethylene glycol monoethyl ether; Propylene glycol monomethyl ether;
2-butoxy ethanol; butyl diethylene glycol ether ethanol;
butoxytriglycol; butylene glycol; hexylene glycol; and propyl propanol. Such solvents may, and preferably are, used in combination with either short chain surfactants, long chain surfactants, or mixtures thereof.
By "short-chain" what is meant herein is surfactants which comprise a Cs-C11 alkyl chain as their hydrophobic portion.
Such short-chain surfactants are accordingly those conventionally used in this field, but with a shorter alkyl chain, and can be of any type. Accordingly, suitable short chain surfactants for use herein include Cs-C11 alkyl sulfates (CS-C11S04), alkyl ether sulfates (C6-C11 (OCH2CH2)eS04), alkyl sulfonates {C6-C11S03), alkyl succinates (C6-C1100CCH2CH2COOZ), alkyl carboxylates (C6-C11COOM), alkyl ether carboxylates (C6-C11 {OCH2CH2)eCOOM), alkyl sarcosinates (C6-C11CON{CH3)R), alkyl sulfo succinates {C6-C1100CCH(S03M)CH2COOZ), amine oxides (C6-C11RR'NO), glucose amides (C6-C11CONR " X), alkylpyrrolidones (C6-C11(C4H60N), alkylpolysaccharides (C6-C110Gg), alkyl alkoxylates (C6-C11 (OCH2CH2)e(OCH2CH2CH2)pOH) and betaines (C6-~ ClIN+(CH3)2CH2C00-). In the formulae in brackets, a and p are independently from 0 to 20 and a+p>0, Z is M or R,M is H or any counterion such as those known in the art, including Na, K,Li, NH4, amine, X is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof, R, R' and R " are Cl-C5 alkyl groups, possibly functionalized with hydroxyl groups, R and R' are preferably Cl-C3, most preferably methyl, R " is preferably 2-hydroxyethyl or 2 hydroxypropyl, G is saccharide, preferably glucose, and g is of from 1.5 to 8. All these surfactants are well known in the art. A more complete disclosure of conventional glucose amides can be found for instance in WO 92-06154 and a more complete disclosure of conventional alkyl polysaccharides can be found for instance in US 4,536,319.
The compositions according to the present invention may comprise any of the above surfactants alone, or any combination thereof.
'r Preferred short chain nonionic surfactants for use herein are alkyl alkoxylates according to the formula C6-C11(OCH2CH2) a (OCH2CH2CH2)pOH, where a and p representing respectively the degree of ethoxylation and propoxylation, are independently of from 0 to 20, and that a+p>0. Most preferred short chain nonionic surfactants for use herein are those where a and p are such that a+p is from 3 to 10, particularly those where p is 0 and a is 3 to e. Also, most preferred short chain nonionic surfactants for use herein are those where said short chain is a hydrocarbon chain comprising from 7 to 11 carbon atoms. Said preferred short chain nonionic surfactants for use herein can be manufactured by the processes well known to the man skilled in the art, such as condensation of the corresponding alcohol and alkylene oxide, but such short chain surfactants are more conveniently commercially available for instance from Sidobre under the trade mark Mergital~C4 (C8E04), from Kolb under the trade marks Imbentin~
AG/810/050 and AG/810/080 (respectively C8-10E05 and C8-10EO8); from Shell under the trade mark Dobanol 91-2.5 (Cg-C11 E02.5), Dobanol 91-6 (C9-C11 E06), Dobanol 91-4-6; from TM TM
Vista Chemicals Vista 1012-52, from EXXON Asopol 91-4.6.
Another preferred class of short chain nonionic surfactants are secondary alcohol ethoxylates according to the formula CH3-(CH2)X-CH-(CH2)y-CH3 I
I
( CHZ-CHZ-0 ) n-H
wherein (X+Y) is from 2 to 10 and the number of ethoxylate groups n is from 1 to 7. Example of commercially available TM
surfactants of this type include the Tergitol S series from Union Carbide.
Preferred short chain anionic surfactants for use herein are C6-C11 alkyl sulfates and C6-C11 alkyl sulfonates, C6-C11 betaines, C6-C11 amine oxides and mixtures thereof.
Most preferred are the C6-Cg alkyl sulfates and sulfonates.
Such short chain anionic surfactants can be made by well known sulphation or sulphonation processes followed by neutralization, but said anionic short chain surfactants are more conveniently commercially available, for instance from Rhone Poulenc under the trade mark Rhodapon ~ OLS, or from Witco under the trade mark Witconate~.
Various nonlimiting examples of bleach activators suitable for use in the compositions of the present invention are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOES) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group . A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551.
Another class of bleach activators comprise the acylated citrate ester described in US5409632. Pref. acylated citrate esters are of the formula -~ CO-OR' R-CO-Oi- CO-OR"
CO-0R'"
wherein R', R " and R " ' are independently selected from the group consisting of H, C1_18 alkyl, C1-lg alkenyl, substituted phenyl, unsubstituted phenyl, alkylphenyl, and alkenylphenyl, and R is selected from the group consisting of Cl -C9 alkyl, C1 -Cg alkenyl, substituted phenyl, r unsubstituted phenyl, alkylphenyl, and alkenylphenyl.
Mixtures of acylated citrate esters are also included herein.
It is best for the efficiency and stability of the peracid precursors for the present invention that R', R " and R " ' should not all be H in a given molecule. Preferably, R is C1 -Cg alkyl, and R', R " and R " ' are selected from the group consisting of H, C1_4 alkyl, and Cl-4 alkenyl, but R', R " and R " ' are not all H. Most preferably, R', R "
and R " ' are methyl or ethyl.
In the bleaching operation, the acylated citrate esters according to the present invention. will react with hydrogen peroxide to yield peracids and citrate esters. The peracid generated depends on the R group which is chosen. Preferred substituted phenyls are sulphophenyls. Preferably, R is Cz -Cg alkyl.
Though not preferred, it is also possible to use acylated citrates which are only partially esterified, i.e. R', R "
or R " ' or combinations thereof are H, the only proviso being that not all three of R', R " and R " ' can be H in a given molecule. In the case where only one of R', R " and R " ' is H, i.e. the acylated citrate ester is a diester, it is preferred to have a "central" diester, i.e. it is preferred that R " is not H. In the case where two of R', R " and R " ' axe H, i.e. the acylated citrate ester is a monoester, it is preferred to have a symmetrical monoester, i.e. a central monoester, i.e. it is preferred that R " is not H. In the case where monoesters are used, it is preferred that the ester chain be rather long, i.e. up to 18 carbon atoms.
Preferred acylated citrate esters are selected from the group consisting of acetyl triethyl citrate, octanoyl trimethyl citrate, acetyl trimethyl citrate, nonanoyl triethyl citrate, hexanoyl triethyl citrate, octanoyl triethyl citrate, nonanoy:l trimethyl citrate, hexanoyl trimethyl citrate and mixtures thereof.
Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S.
Patent 4,966,723, issued October 30, 1990. A highly preferred activator of the benzoxazin-type is:
O
II
o' ..~ o N
Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
O O
O C-C H2-C H2\ O C-C H2- ~ HZ
Rs-C-NBC H2-C H2 C H2 R6 C-N.~ C H2-C H2 wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl va:lerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Any alkaline materials is suitable for use in the present invention. Preferred alkaline materials are selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ammonium silicate, sodium bicarbonate, borax, monoethanolamine borate, monoethanolamine triethanolamine, and mixtures thereof.
In general the spot treating composition comprises from 0.1% to 10%, preferably 0.5% to 3% by weight of the alkaline material. Preferably the pH is greater than 8, more preferably greater than 9, and most preferably greater than 10. pH of the neat compositions was measured by means TM
of a portable pH meter from Knick (Portamess 752).
By "long-chain" what is meant herein is surfactants having an alkyl chain, the alkyl chain comprising 12, or more than 12 carbon atoms.
Non-limiting examples of long-chain surfactants useful herein include the conventional C12-C18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C12-C20 alkyl sulfates ("AS"), the C12-Clg secondary (2,3) alkyl sulfates of the fomula CH3(CH2)x(CHOS03-M+) CH3 and CH3 (CH2)y(CHOS03-M+)CH2CH3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C12-Clg alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), C12-Clg alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C12-18 glycerol ethers, the C12-Clg alkyl polyglycosides and their corresponding sulfated polyglycosides the C12-Clg alpha-sulfonated fatty acid esters methyl ester sulphonate (MES), and oleyol sarcosinates. The conventional nonionic and amphoteric surfactants such as the C12-Clg alkyl ethoxylates ("AE") particulary preferred are C12-C16 fatty alcohol polyglycol ethers or ethoxylated primary alcohols with EO 2-7 (especially ethoxylates and mixed ethoxy/propoxy), C12-Clg betaines and sulfobetaines ("sultaines"), C12-C18 amine oxides, and the like, can also be included in the overall compositions. The C12-C1B N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-Clg N-methylglucamides. See WO 92/06154. Other sugar-derived surfactants include the N-alkoxy polyhhydroxy fatty acid amides, such as C1~-Clg N-(3-methoxypropyl) glucamide.
The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C12-C~0 conventional soaps may also be used. If high sudsing is desired, the branched-chain C12-C16 soaps rnay be used. Mixtures of anionic and nonionic surfactants are espicially useful. Other conventional useful surfactants are listed in standard texts.
A particularly preferred composition according to the present invention comprises from 5% to 50% by weight of a mixed nonionic system comprising first, short-chain nonionic surfactant and second, long-chain nonionic surfactant. More preferably the composition comprises from 10% to 40% by weight of the mixed nonionic surfactant, and most preferably from 15% to 30%. The nonionic system preferably has an overall hydrophilic-lipophilic balance (HLB) value of from 2 to 16, more preferably from 8 to 14, most preferably from 9 to 10. Furthermore it is preferred that the ratio of first surfactant to second surfactant is from 1:10 to 10:1, more preferably from 2:3 to 3:1, and most preferably about 1:1.
The detergent composition of the present invention is useful in various known and conventional cleaning methods. ' However a preferred cleaning method comprises the steps of applying the detergent composition to the spot or stain;
placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain; and applying heat, pressure, or heat and pressure to the textile fabric in the region of the spot or stain; so that some or alI of the spot or stain is absorbed into the absorbent layer.
A still more preferred cleaning method comprises the steps of .
(a) applying the detergent composition to a spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain and a first means for transferring some or all of the spot or stain into the absorbent 3ayer; optionally also applying a peroxide bleaching agent and subsequently (b) applying a hydrophilic solvent or water, to the textile fabric in the region of the spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain and the step of applying heat to the textile fabric in the region of the spot or stain.
The application of heat or pressure, or both, may be achieved by any means, but is most preferably achieved by a hand-held device such as an iron. A conventional iron having a hot-plate fixed to a body is a highly preferred hand held device. The hot-plate is heated most commonly by a electrical means, and may have a means for controlling the temperature. A supply of water or steam may also be provided by the iron. Most preferably the absorbent layer is placed on a flat surface, such as an ironing board, and the stained or soiled textile fabric is laid flat on top of, and in contact with, the absorbent layer. The iron can then be easily applied to the textile fabric in the region of the stain or spot in order to ensure complete, or substantially complete, transfer of the stain or spot into the absorbent layer. The iron is preferably operated at a temperature of from 40°C to 200°C, more preferably from 40°C to 180°C.
An alternative device for applying heat or pressure is a heated roller or any other heated applicator. The roller or applicator may also be provided with a supply of the detergent composition.
Suitable applicators include a steam iron with suction brush attachment, such as that disclosed in EP-A-0 493 348, and a thermoelectric applicator, such as that disclosed in EP-A-0 552 397. Also suitable is a steam iron with atomiser, such as that disclose in EP-A-0 629 736 wherein the detergent composition may optionally be stored in the iron and delivered directly onto the textile fabrics by means of the atomiser.
Without wishing to be bound by theory it is believed that hydrophobic stains are first rendered hydrophilic by applying a detergent composition, optionally with a gentle rubbing action. Greasy stains which contain hydroxyl groups are deprotoneated at high pH and are thus rendered more easy to solubilize in the detergent solution. Higher pH can also induce soll peptization on some food stains.
The stains are in effect broken down, and rendered easier to remove. The benefits of high pH can be particularly observed when before or after application of the detergent composition, another composition containing a bleaching species is applied on the stain. Indeed, conventional peroxide bleaching technologies have an increased reactivity with pH. Water is then applied to the stain, again, optionally with a gentle rubbing action. The stain is removed by laying the stained fabric adjacent to an absorbent layer. The stain, which has been rendered more - hydrophilic by the treatment, is transferred to the absorbent layer.
Textile fabrics are any materials made from cloth, including garments such as shirts, blouses, socks, skirts, , trousers, jackets, underwear etc, and also including tablecloths, towels, curtains etc. The definition of textile fabrics as used herein does not include carpets and similar floor coverings.
Textile fabrics which are to be used in the present invention are commonly made by weaving or knitting. Many different fibres may be used to produce woven, knitted or other types. of textile fabric including synthetic fibres (such as polyester, polyamide, etc.) and natural fibres from plants (such as cotton, hemp) and from animals (such as wool, angora, silk). Blends of different fibres are also commonly used.
J
EXAMPLES
In the examples, all compositions are expressed as % by weight (unless otherwise stated).
In the examples, Shellsol ° is a mixture of C8-C11 isoparaffins with 5% aliphatic C7 ester.
Dobanol ° is a ethoxylated primary alcohol with an average of 3E0, supplied by Shell.
TM
Lutensol AE21 is C13-15 ethoxylated alcohol with an average of 21E0.
Dehydol ° is a fatty alcohol polyglycol ether octyl with an average of 4E0, supplied by Fienkel.
Alkyl sulphate, C6AS, has an average of 6 carbon atoms in the alkyl chain.
DTPMP is diethylene triamine penta methylene phosphoric acid Example Example Example Example Shellsol 20 - 20 20 D-Limonene - 24 - -Sodium paraffin 0.2 0.4 0.2 0.2 sulphonate Dobanol 23-3 0.2 0.4 0.2 0.2 Dobanol 25-3 5 10 5 5 Lutensol AE21 0.3 0.6 0.3 0.3 Dehydol C8E04 5 10 5 -C6AS - - _ S
Sodium hydroxide 3.1 6.2 - 3.1 Monoethanolamine - - 3 -Sodium carbonate 0.7 1.4 - -Sodium bisulfite - - 1 _ Citric acid 3 6 - 3 DTPMP 0.75 1.5 - 0.?S
Acetyl Triethyl 2 4 2 2 Citrate Water Balance Balance Balance Balance In Example 4 the C6-AS was replaced in turn by C8-LAS, C8-ethylhexyl AS, C8-octylsulphonate, C8 dimethylamine oxide, C71E06.5 and sodium cumene sulphonate.
All of the compositions of the examples had a final pH of 10.
A set of polycotton swatches (50mm square) were soiled with make-up, chocolate sauce and tomato sauce. The stain was left to age for a day, in the dark, at normal room temperature (c.a. 20oC, 60%RH). Each soiled swatch was cleaned by the following method:
1. The stained area was placed directly upon a strip of absorbent paper (the paper used was the absorbent core of a diaper) .
2. I ml of the composition of Example 1 was dripped on to the stained area.
3. The stained area was brushed with a conventional electrical toothbrush for 10 seconds (the toothbrush used, a Braun~ dental d3, was one normally intended for daily oral care).
4. 1 ml of the peroxide composition of example 5 was dripped onto the stained area and the stained area was again brushed with the toothbrush.
5. Pressure and heat were applied using an iron set at a temperature of 140°C for 10 seconds. A typical ironing pressure, as normally used for removing wrinkles in fabrics, was used.
It is the objective of the present invention to improve the removal of bleachable stains through the application of the composition of the present invention and the application of a bleaching compound, preferably a peroxide compound.
Summary c>f the Invention The objective of the present invention is achieved by providing a cleaning composition which further comprises a bleach activator so that cleaning performance for bleachable stains is enhanced.
In a preferred embodiment there is provided a microemulsion cleaning composition having a pH greater than 10 which is an oil-in-water or water-in-oil microemulsion, comprising:
(i) from 5o to 250 of a non-aqueous hydrophobic solvent selected from the group consisting of deodorised kerosene, chlorinated hydrocarbons, 1,1,1-trichloroethane, perchloroethylene, methylene chloride, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, 2-butoxy ethanol, butyl diethylene glycol ether ethanol, butoxytriglycol, butylene glycol, hexylene glycol, and 2a propyl propanol; (ii) at least 5% of a first anionic or nonionic surfactant; characterised in that the cleaning composition further comprises (iii) a bleach activator present in an amount in a range of from 0.1% to 10% by weight, wherein said bleach activator is selected from the group consisting of amido-derived bleach activators of the formulae selected from the group consisting of R1N (RS) C (0) RZC (0) L and R1C (0) N (R5) RZC (0) L wherein R1 is an alkyl group containing from 6 to 12 atoms, RZ is an alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is a leaving group; acylated citrate ester bleach activators, benzoxazin bleach activators; acyl lactum bleach activators; and mixtures thereof; and (iv) 5% to 95% water.
The invention also relates to a method for treating a spot or stain on a textile fabric using the cleaning compositions of the invention.
Detailed Description of the Invention t Hydrophobic solvents are an essential feature of the compostions of the present invention. Preferred hydrophobic solvents are defined in terms of Hansen . parameters. A hydrophobic solvent as defined herein is considered to be a solvent having Hansen hydrogen bonding cohesion parameter dH below 18 tJoule/cm3)0.5 - preferred hydrophobic solvents have a Hansen hydrogen bonding cohesion parameter dH below 12 (Joule/cm3)0.5 and a Hansen polar parameter dP below 8 (Joule/cm3)0.5 .
Preferred solvents for use comprise mixtures of hydrocarbons with a flash point no lower than 70°C, an initial boiling point no lower than 130°C, preferably no lower than 145°C and a solidification point not above 20°C
and aliphatic fatty acid esters. More preferred solvents would be alkanes or alkenes with a chain length above C7, and particularly alkanes and alkenes with an average of C8 to C20 atoms. Particularly preferred hydrophobic solvents are deodorised kerosine; solvent naphta; chlorinated hydrocarbons; and terpenes. Even more preferred are paraffins; isoparaffins; naphthenes; aromatics; olefins;
1,1,1-trichloroethane perchloroethylene; methylene chloride; Shellsol SS~ mixture (C8-C11 isoparaffin + 5%
aliphatic C7 ester); D-Limonene; and Glidsafe~ supplied by Glidsol. Solvents are used in the detergent compositions of the present invention preferably at a level of from 3% to 90%, more preferably from 4% to 45%, and most preferably from 5% to 25% by weight of the detergent composition.
Other solvents having a Hansen parameter of dH less than 18 ' (~Toule/cm3)0~5 include glycol ethers, more preferably glycol ethers based upon ethylene oxide, propylene oxide, or mixtures thereof. Particularly preferred are ethylene glycol monoethyl ether; Propylene glycol monomethyl ether;
2-butoxy ethanol; butyl diethylene glycol ether ethanol;
butoxytriglycol; butylene glycol; hexylene glycol; and propyl propanol. Such solvents may, and preferably are, used in combination with either short chain surfactants, long chain surfactants, or mixtures thereof.
By "short-chain" what is meant herein is surfactants which comprise a Cs-C11 alkyl chain as their hydrophobic portion.
Such short-chain surfactants are accordingly those conventionally used in this field, but with a shorter alkyl chain, and can be of any type. Accordingly, suitable short chain surfactants for use herein include Cs-C11 alkyl sulfates (CS-C11S04), alkyl ether sulfates (C6-C11 (OCH2CH2)eS04), alkyl sulfonates {C6-C11S03), alkyl succinates (C6-C1100CCH2CH2COOZ), alkyl carboxylates (C6-C11COOM), alkyl ether carboxylates (C6-C11 {OCH2CH2)eCOOM), alkyl sarcosinates (C6-C11CON{CH3)R), alkyl sulfo succinates {C6-C1100CCH(S03M)CH2COOZ), amine oxides (C6-C11RR'NO), glucose amides (C6-C11CONR " X), alkylpyrrolidones (C6-C11(C4H60N), alkylpolysaccharides (C6-C110Gg), alkyl alkoxylates (C6-C11 (OCH2CH2)e(OCH2CH2CH2)pOH) and betaines (C6-~ ClIN+(CH3)2CH2C00-). In the formulae in brackets, a and p are independently from 0 to 20 and a+p>0, Z is M or R,M is H or any counterion such as those known in the art, including Na, K,Li, NH4, amine, X is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof, R, R' and R " are Cl-C5 alkyl groups, possibly functionalized with hydroxyl groups, R and R' are preferably Cl-C3, most preferably methyl, R " is preferably 2-hydroxyethyl or 2 hydroxypropyl, G is saccharide, preferably glucose, and g is of from 1.5 to 8. All these surfactants are well known in the art. A more complete disclosure of conventional glucose amides can be found for instance in WO 92-06154 and a more complete disclosure of conventional alkyl polysaccharides can be found for instance in US 4,536,319.
The compositions according to the present invention may comprise any of the above surfactants alone, or any combination thereof.
'r Preferred short chain nonionic surfactants for use herein are alkyl alkoxylates according to the formula C6-C11(OCH2CH2) a (OCH2CH2CH2)pOH, where a and p representing respectively the degree of ethoxylation and propoxylation, are independently of from 0 to 20, and that a+p>0. Most preferred short chain nonionic surfactants for use herein are those where a and p are such that a+p is from 3 to 10, particularly those where p is 0 and a is 3 to e. Also, most preferred short chain nonionic surfactants for use herein are those where said short chain is a hydrocarbon chain comprising from 7 to 11 carbon atoms. Said preferred short chain nonionic surfactants for use herein can be manufactured by the processes well known to the man skilled in the art, such as condensation of the corresponding alcohol and alkylene oxide, but such short chain surfactants are more conveniently commercially available for instance from Sidobre under the trade mark Mergital~C4 (C8E04), from Kolb under the trade marks Imbentin~
AG/810/050 and AG/810/080 (respectively C8-10E05 and C8-10EO8); from Shell under the trade mark Dobanol 91-2.5 (Cg-C11 E02.5), Dobanol 91-6 (C9-C11 E06), Dobanol 91-4-6; from TM TM
Vista Chemicals Vista 1012-52, from EXXON Asopol 91-4.6.
Another preferred class of short chain nonionic surfactants are secondary alcohol ethoxylates according to the formula CH3-(CH2)X-CH-(CH2)y-CH3 I
I
( CHZ-CHZ-0 ) n-H
wherein (X+Y) is from 2 to 10 and the number of ethoxylate groups n is from 1 to 7. Example of commercially available TM
surfactants of this type include the Tergitol S series from Union Carbide.
Preferred short chain anionic surfactants for use herein are C6-C11 alkyl sulfates and C6-C11 alkyl sulfonates, C6-C11 betaines, C6-C11 amine oxides and mixtures thereof.
Most preferred are the C6-Cg alkyl sulfates and sulfonates.
Such short chain anionic surfactants can be made by well known sulphation or sulphonation processes followed by neutralization, but said anionic short chain surfactants are more conveniently commercially available, for instance from Rhone Poulenc under the trade mark Rhodapon ~ OLS, or from Witco under the trade mark Witconate~.
Various nonlimiting examples of bleach activators suitable for use in the compositions of the present invention are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOES) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group . A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551.
Another class of bleach activators comprise the acylated citrate ester described in US5409632. Pref. acylated citrate esters are of the formula -~ CO-OR' R-CO-Oi- CO-OR"
CO-0R'"
wherein R', R " and R " ' are independently selected from the group consisting of H, C1_18 alkyl, C1-lg alkenyl, substituted phenyl, unsubstituted phenyl, alkylphenyl, and alkenylphenyl, and R is selected from the group consisting of Cl -C9 alkyl, C1 -Cg alkenyl, substituted phenyl, r unsubstituted phenyl, alkylphenyl, and alkenylphenyl.
Mixtures of acylated citrate esters are also included herein.
It is best for the efficiency and stability of the peracid precursors for the present invention that R', R " and R " ' should not all be H in a given molecule. Preferably, R is C1 -Cg alkyl, and R', R " and R " ' are selected from the group consisting of H, C1_4 alkyl, and Cl-4 alkenyl, but R', R " and R " ' are not all H. Most preferably, R', R "
and R " ' are methyl or ethyl.
In the bleaching operation, the acylated citrate esters according to the present invention. will react with hydrogen peroxide to yield peracids and citrate esters. The peracid generated depends on the R group which is chosen. Preferred substituted phenyls are sulphophenyls. Preferably, R is Cz -Cg alkyl.
Though not preferred, it is also possible to use acylated citrates which are only partially esterified, i.e. R', R "
or R " ' or combinations thereof are H, the only proviso being that not all three of R', R " and R " ' can be H in a given molecule. In the case where only one of R', R " and R " ' is H, i.e. the acylated citrate ester is a diester, it is preferred to have a "central" diester, i.e. it is preferred that R " is not H. In the case where two of R', R " and R " ' axe H, i.e. the acylated citrate ester is a monoester, it is preferred to have a symmetrical monoester, i.e. a central monoester, i.e. it is preferred that R " is not H. In the case where monoesters are used, it is preferred that the ester chain be rather long, i.e. up to 18 carbon atoms.
Preferred acylated citrate esters are selected from the group consisting of acetyl triethyl citrate, octanoyl trimethyl citrate, acetyl trimethyl citrate, nonanoyl triethyl citrate, hexanoyl triethyl citrate, octanoyl triethyl citrate, nonanoy:l trimethyl citrate, hexanoyl trimethyl citrate and mixtures thereof.
Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S.
Patent 4,966,723, issued October 30, 1990. A highly preferred activator of the benzoxazin-type is:
O
II
o' ..~ o N
Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
O O
O C-C H2-C H2\ O C-C H2- ~ HZ
Rs-C-NBC H2-C H2 C H2 R6 C-N.~ C H2-C H2 wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl va:lerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
Any alkaline materials is suitable for use in the present invention. Preferred alkaline materials are selected from the group consisting of potassium hydroxide, sodium hydroxide, ammonium hydroxide, ammonium silicate, sodium bicarbonate, borax, monoethanolamine borate, monoethanolamine triethanolamine, and mixtures thereof.
In general the spot treating composition comprises from 0.1% to 10%, preferably 0.5% to 3% by weight of the alkaline material. Preferably the pH is greater than 8, more preferably greater than 9, and most preferably greater than 10. pH of the neat compositions was measured by means TM
of a portable pH meter from Knick (Portamess 752).
By "long-chain" what is meant herein is surfactants having an alkyl chain, the alkyl chain comprising 12, or more than 12 carbon atoms.
Non-limiting examples of long-chain surfactants useful herein include the conventional C12-C18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C12-C20 alkyl sulfates ("AS"), the C12-Clg secondary (2,3) alkyl sulfates of the fomula CH3(CH2)x(CHOS03-M+) CH3 and CH3 (CH2)y(CHOS03-M+)CH2CH3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C12-Clg alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), C12-Clg alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C12-18 glycerol ethers, the C12-Clg alkyl polyglycosides and their corresponding sulfated polyglycosides the C12-Clg alpha-sulfonated fatty acid esters methyl ester sulphonate (MES), and oleyol sarcosinates. The conventional nonionic and amphoteric surfactants such as the C12-Clg alkyl ethoxylates ("AE") particulary preferred are C12-C16 fatty alcohol polyglycol ethers or ethoxylated primary alcohols with EO 2-7 (especially ethoxylates and mixed ethoxy/propoxy), C12-Clg betaines and sulfobetaines ("sultaines"), C12-C18 amine oxides, and the like, can also be included in the overall compositions. The C12-C1B N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-Clg N-methylglucamides. See WO 92/06154. Other sugar-derived surfactants include the N-alkoxy polyhhydroxy fatty acid amides, such as C1~-Clg N-(3-methoxypropyl) glucamide.
The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C12-C~0 conventional soaps may also be used. If high sudsing is desired, the branched-chain C12-C16 soaps rnay be used. Mixtures of anionic and nonionic surfactants are espicially useful. Other conventional useful surfactants are listed in standard texts.
A particularly preferred composition according to the present invention comprises from 5% to 50% by weight of a mixed nonionic system comprising first, short-chain nonionic surfactant and second, long-chain nonionic surfactant. More preferably the composition comprises from 10% to 40% by weight of the mixed nonionic surfactant, and most preferably from 15% to 30%. The nonionic system preferably has an overall hydrophilic-lipophilic balance (HLB) value of from 2 to 16, more preferably from 8 to 14, most preferably from 9 to 10. Furthermore it is preferred that the ratio of first surfactant to second surfactant is from 1:10 to 10:1, more preferably from 2:3 to 3:1, and most preferably about 1:1.
The detergent composition of the present invention is useful in various known and conventional cleaning methods. ' However a preferred cleaning method comprises the steps of applying the detergent composition to the spot or stain;
placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain; and applying heat, pressure, or heat and pressure to the textile fabric in the region of the spot or stain; so that some or alI of the spot or stain is absorbed into the absorbent layer.
A still more preferred cleaning method comprises the steps of .
(a) applying the detergent composition to a spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain and a first means for transferring some or all of the spot or stain into the absorbent 3ayer; optionally also applying a peroxide bleaching agent and subsequently (b) applying a hydrophilic solvent or water, to the textile fabric in the region of the spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain and the step of applying heat to the textile fabric in the region of the spot or stain.
The application of heat or pressure, or both, may be achieved by any means, but is most preferably achieved by a hand-held device such as an iron. A conventional iron having a hot-plate fixed to a body is a highly preferred hand held device. The hot-plate is heated most commonly by a electrical means, and may have a means for controlling the temperature. A supply of water or steam may also be provided by the iron. Most preferably the absorbent layer is placed on a flat surface, such as an ironing board, and the stained or soiled textile fabric is laid flat on top of, and in contact with, the absorbent layer. The iron can then be easily applied to the textile fabric in the region of the stain or spot in order to ensure complete, or substantially complete, transfer of the stain or spot into the absorbent layer. The iron is preferably operated at a temperature of from 40°C to 200°C, more preferably from 40°C to 180°C.
An alternative device for applying heat or pressure is a heated roller or any other heated applicator. The roller or applicator may also be provided with a supply of the detergent composition.
Suitable applicators include a steam iron with suction brush attachment, such as that disclosed in EP-A-0 493 348, and a thermoelectric applicator, such as that disclosed in EP-A-0 552 397. Also suitable is a steam iron with atomiser, such as that disclose in EP-A-0 629 736 wherein the detergent composition may optionally be stored in the iron and delivered directly onto the textile fabrics by means of the atomiser.
Without wishing to be bound by theory it is believed that hydrophobic stains are first rendered hydrophilic by applying a detergent composition, optionally with a gentle rubbing action. Greasy stains which contain hydroxyl groups are deprotoneated at high pH and are thus rendered more easy to solubilize in the detergent solution. Higher pH can also induce soll peptization on some food stains.
The stains are in effect broken down, and rendered easier to remove. The benefits of high pH can be particularly observed when before or after application of the detergent composition, another composition containing a bleaching species is applied on the stain. Indeed, conventional peroxide bleaching technologies have an increased reactivity with pH. Water is then applied to the stain, again, optionally with a gentle rubbing action. The stain is removed by laying the stained fabric adjacent to an absorbent layer. The stain, which has been rendered more - hydrophilic by the treatment, is transferred to the absorbent layer.
Textile fabrics are any materials made from cloth, including garments such as shirts, blouses, socks, skirts, , trousers, jackets, underwear etc, and also including tablecloths, towels, curtains etc. The definition of textile fabrics as used herein does not include carpets and similar floor coverings.
Textile fabrics which are to be used in the present invention are commonly made by weaving or knitting. Many different fibres may be used to produce woven, knitted or other types. of textile fabric including synthetic fibres (such as polyester, polyamide, etc.) and natural fibres from plants (such as cotton, hemp) and from animals (such as wool, angora, silk). Blends of different fibres are also commonly used.
J
EXAMPLES
In the examples, all compositions are expressed as % by weight (unless otherwise stated).
In the examples, Shellsol ° is a mixture of C8-C11 isoparaffins with 5% aliphatic C7 ester.
Dobanol ° is a ethoxylated primary alcohol with an average of 3E0, supplied by Shell.
TM
Lutensol AE21 is C13-15 ethoxylated alcohol with an average of 21E0.
Dehydol ° is a fatty alcohol polyglycol ether octyl with an average of 4E0, supplied by Fienkel.
Alkyl sulphate, C6AS, has an average of 6 carbon atoms in the alkyl chain.
DTPMP is diethylene triamine penta methylene phosphoric acid Example Example Example Example Shellsol 20 - 20 20 D-Limonene - 24 - -Sodium paraffin 0.2 0.4 0.2 0.2 sulphonate Dobanol 23-3 0.2 0.4 0.2 0.2 Dobanol 25-3 5 10 5 5 Lutensol AE21 0.3 0.6 0.3 0.3 Dehydol C8E04 5 10 5 -C6AS - - _ S
Sodium hydroxide 3.1 6.2 - 3.1 Monoethanolamine - - 3 -Sodium carbonate 0.7 1.4 - -Sodium bisulfite - - 1 _ Citric acid 3 6 - 3 DTPMP 0.75 1.5 - 0.?S
Acetyl Triethyl 2 4 2 2 Citrate Water Balance Balance Balance Balance In Example 4 the C6-AS was replaced in turn by C8-LAS, C8-ethylhexyl AS, C8-octylsulphonate, C8 dimethylamine oxide, C71E06.5 and sodium cumene sulphonate.
All of the compositions of the examples had a final pH of 10.
A set of polycotton swatches (50mm square) were soiled with make-up, chocolate sauce and tomato sauce. The stain was left to age for a day, in the dark, at normal room temperature (c.a. 20oC, 60%RH). Each soiled swatch was cleaned by the following method:
1. The stained area was placed directly upon a strip of absorbent paper (the paper used was the absorbent core of a diaper) .
2. I ml of the composition of Example 1 was dripped on to the stained area.
3. The stained area was brushed with a conventional electrical toothbrush for 10 seconds (the toothbrush used, a Braun~ dental d3, was one normally intended for daily oral care).
4. 1 ml of the peroxide composition of example 5 was dripped onto the stained area and the stained area was again brushed with the toothbrush.
5. Pressure and heat were applied using an iron set at a temperature of 140°C for 10 seconds. A typical ironing pressure, as normally used for removing wrinkles in fabrics, was used.
6. 1 ml of distilled water was dripped onto the stained area.
7. Step 5. was repeated followed by the further addition of ' 2m1 of distilled water.
8. The swatch was dried and smoothed.
The method of cleaning was repeated on stained swatches using the compositions of Examples 2 to 4 in place of the composition of Example 1.
Example 5 - peroxide composition C10 alkyl sulphate 1.2 Dobanol 23-3 1.1 Dobanol 91-10 1.6 Polyvinyl pyrrolidone 0.2 Hydrogen peroxide 6.8 TM
IsoFol 12 0.5 DTPMP 0.2 Sulphuric acid to pH 4 Water to balance IsoFol 12 is 2 butyloctanol from Condea.
The method of cleaning was repeated on stained swatches using the compositions of Examples 2 to 4 in place of the composition of Example 1.
Example 5 - peroxide composition C10 alkyl sulphate 1.2 Dobanol 23-3 1.1 Dobanol 91-10 1.6 Polyvinyl pyrrolidone 0.2 Hydrogen peroxide 6.8 TM
IsoFol 12 0.5 DTPMP 0.2 Sulphuric acid to pH 4 Water to balance IsoFol 12 is 2 butyloctanol from Condea.
Claims (9)
1. A microemulsion cleaning composition having a pH greater than 10 which is an oil-in-water or water-in-oil microemulsion, comprising:
(i) from 5% to 25% of a non-aqueous hydrophobic solvent selected from the group consisting of deodorised kerosene, chlorinated hydrocarbons, 1,1,1-trichloroethane, perchloroethylene, methylene chloride, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, 2-butoxy ethanol, butyl diethylene glycol ether ethanol, butoxytriglycol, butylene glycol, hexylene glycol, and propyl propanol;
(ii) at least 5% of a first anionic or nonionic surfactant;
characterised in that the cleaning composition further comprises (iii) a bleach activator present in an amount in a range of from 0.1% to 10% by weight, wherein said bleach activator is selected from the group consisting of amido-derived bleach activators of the formulae selected from the group consisting of R1N(R5)C(O)R2C(O)L and R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from 6 to 12 atoms, R2 is an alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is a leaving group; acylated citrate ester bleach activators; benzoxazin bleach activators; aryl lactum bleach activators; and mixtures thereof; and (iv) 5% to 95% water.
(i) from 5% to 25% of a non-aqueous hydrophobic solvent selected from the group consisting of deodorised kerosene, chlorinated hydrocarbons, 1,1,1-trichloroethane, perchloroethylene, methylene chloride, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, 2-butoxy ethanol, butyl diethylene glycol ether ethanol, butoxytriglycol, butylene glycol, hexylene glycol, and propyl propanol;
(ii) at least 5% of a first anionic or nonionic surfactant;
characterised in that the cleaning composition further comprises (iii) a bleach activator present in an amount in a range of from 0.1% to 10% by weight, wherein said bleach activator is selected from the group consisting of amido-derived bleach activators of the formulae selected from the group consisting of R1N(R5)C(O)R2C(O)L and R1C(O)N(R5)R2C(O)L
wherein R1 is an alkyl group containing from 6 to 12 atoms, R2 is an alkylene containing from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is a leaving group; acylated citrate ester bleach activators; benzoxazin bleach activators; aryl lactum bleach activators; and mixtures thereof; and (iv) 5% to 95% water.
2. A cleaning composition according to claim 1 wherein the first surfactant has an alkyl chain, the length of the alkyl chain being C11 or less; and further comprising (v) second surfactant having an alkyl chain, the length of the alkyl chain being C12 or more.
3. A cleaning composition according to claim 2 wherein the second surfactant is selected from the group consisting of C12-C16 fatty alcohol polyglycol ethers and ethoxylated primary alcohols with 2 to 7 ethoxylation.
4. A cleaning composition according to claim 2 comprising from 5% to 50% by weight of a mixed nonionic surfactant system comprising the first and second surfactants, the mixed nonionic surfactant system having an overall hydrophilic-lipophilic balance (HLB) value of from 2 to 16.
5. A cleaning composition according to claim 2 wherein the molar ratio of first surfactant to second surfactant is from 1:10 to 10:1.
6. A cleaning composition according to claim 1 wherein the first surfactant is selected from the group consisting of C6-C11 alkyl alkoxylates according to the formula (OCH2CH2)e(OCH(CH3)CH2)p OH where e+p ranges from 3 to 10, C6-C11 secondary alcohol ethoxylates, C6-C11 alkyl sulphonates, C6-C11 alkyl sulphates, C6-C11 amine oxides, and mixtures thereof.
7. A method of treating a spot or stain on a textile fabric comprising the steps of:
applying the detergent composition as defined in any one of claims 1 to 6 to the spot or stain;
placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain; and applying heat, pressure, or heat and pressure, to the textile fabric in the region of the spot or stain, so that some or all of the spot or stain is absorbed into the absorbent layer.
applying the detergent composition as defined in any one of claims 1 to 6 to the spot or stain;
placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain; and applying heat, pressure, or heat and pressure, to the textile fabric in the region of the spot or stain, so that some or all of the spot or stain is absorbed into the absorbent layer.
8. A method according to claim 7 comprising the steps of:
(a) applying the detergent composition to the spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain for transferring some or all of the spot or stain into the absorbent layer;
and subsequently (b) applying a hydrophilic solvent, or water, to the textile fabric in the region of the spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain for transferring some or all of the spot or stain into the absorbent layer.
(a) applying the detergent composition to the spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain for transferring some or all of the spot or stain into the absorbent layer;
and subsequently (b) applying a hydrophilic solvent, or water, to the textile fabric in the region of the spot or stain and placing an absorbent layer adjacent to the textile fabric in the region of the spot or stain for transferring some or all of the spot or stain into the absorbent layer.
9. A method according to claim 8, comprises the further step of applying heat to the textile fabric in the region of the spot or stain using a hand-held iron.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95118617.0 | 1995-11-27 | ||
EP95118617 | 1995-11-27 | ||
PCT/US1996/014772 WO1997020095A1 (en) | 1995-11-27 | 1996-09-16 | Composition for treating stains on laundry items and methods of treatment |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2238482A1 CA2238482A1 (en) | 1997-06-05 |
CA2238482C true CA2238482C (en) | 2005-04-12 |
Family
ID=8219839
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002238620A Expired - Fee Related CA2238620C (en) | 1995-11-27 | 1996-09-16 | Composition for treating stains on laundry items and method of treatment |
CA002238482A Expired - Fee Related CA2238482C (en) | 1995-11-27 | 1996-09-16 | Composition for treating stains on laundry items and methods of treatment |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002238620A Expired - Fee Related CA2238620C (en) | 1995-11-27 | 1996-09-16 | Composition for treating stains on laundry items and method of treatment |
Country Status (14)
Country | Link |
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EP (2) | EP0871808B1 (en) |
JP (2) | JP3085986B2 (en) |
AR (3) | AR004771A1 (en) |
AT (2) | ATE232919T1 (en) |
AU (4) | AU7109896A (en) |
BR (3) | BR9612283A (en) |
CA (2) | CA2238620C (en) |
DE (1) | DE69626311T2 (en) |
EG (1) | EG20922A (en) |
ES (1) | ES2188785T3 (en) |
MX (3) | MX9804177A (en) |
NO (2) | NO982359D0 (en) |
WO (3) | WO1997020095A1 (en) |
ZA (2) | ZA969921B (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
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US5891197A (en) * | 1996-08-02 | 1999-04-06 | The Proctor & Gamble Company | Stain receiver for dry cleaning process |
US6855172B2 (en) | 1998-10-13 | 2005-02-15 | Dry, Inc. | Dry-cleaning article, composition and methods |
JP4005092B2 (en) | 2004-08-20 | 2007-11-07 | 東京応化工業株式会社 | Cleaning solvent |
US7757340B2 (en) | 2005-03-25 | 2010-07-20 | S.C. Johnson & Son, Inc. | Soft-surface remediation device and method of using same |
TWI400330B (en) | 2005-12-28 | 2013-07-01 | Kao Corp | Liquid detergent |
ES2662323T3 (en) | 2010-07-07 | 2018-04-06 | Dalli-Werke Gmbh & Co. Kg | Composition of prewash stains for local laundry application |
JP5544256B2 (en) * | 2010-09-21 | 2014-07-09 | 花王株式会社 | Hard surface cleaning method |
GB201021822D0 (en) * | 2010-12-23 | 2011-02-02 | Reckitt & Colman Overseas | Cleaning composition and method |
JP2012131949A (en) * | 2010-12-24 | 2012-07-12 | Idemitsu Kosan Co Ltd | Emulsion composition containing isoparafin |
ES2622230T3 (en) | 2011-06-17 | 2017-07-06 | Dalli-Werke Gmbh & Co. Kg | Detergent composition comprising dirt release polymers with improved storage stability |
RU2642781C2 (en) * | 2013-09-06 | 2018-01-26 | Дзе Проктер Энд Гэмбл Компани | Capsules, containing water-soluble fibre walls materials and methods of its manufacture |
FR3047488B1 (en) * | 2016-02-05 | 2020-02-28 | Laboratoires Anios | DETERGENT COMPOSITIONS FOR CLEANING IN THE COSMETIC AND PHARMACEUTICAL INDUSTRY. |
RU2751765C2 (en) * | 2018-12-21 | 2021-07-16 | Светлана Борисовна Узенькова | Method of cleaning products made of natural and artificial leather, natural and artificial fur and lining fabric of products |
JP7332286B2 (en) | 2018-12-26 | 2023-08-23 | 花王株式会社 | Textile treatment method |
Family Cites Families (20)
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US495428A (en) * | 1893-04-11 | Furnace-mouth feed-water heater | ||
CA965913A (en) * | 1971-02-03 | 1975-04-15 | Paul A. Boulus | Thick covering textile cleaning process and cleaning pad |
US3748268A (en) * | 1972-03-27 | 1973-07-24 | Minnesota Mining & Mfg | Spot and stain removing composition |
GB1518676A (en) * | 1975-10-30 | 1978-07-19 | Procter & Gamble Ltd | Detergent compositions |
US4199482A (en) * | 1977-03-31 | 1980-04-22 | Colgate-Palmolive Company | Laundry pre-spotter composition and method of using same |
DE2903061A1 (en) * | 1979-01-26 | 1980-08-07 | Heliotronic Gmbh | METHOD FOR PRODUCING LARGE CRYSTALLINE, PREFERRED ORIENTED SILICON FILMS |
DE2939810A1 (en) * | 1979-10-01 | 1981-04-16 | Henkel KGaA, 4000 Düsseldorf | SPRAY CLEANER SUITABLE FOR TEXTILE TREATMENT |
US4336024A (en) * | 1980-02-22 | 1982-06-22 | Airwick Industries, Inc. | Process for cleaning clothes at home |
US4412934A (en) * | 1982-06-30 | 1983-11-01 | The Procter & Gamble Company | Bleaching compositions |
EP0125781B1 (en) * | 1983-04-14 | 1987-08-12 | Interox Chemicals Limited | Peroxygen compounds |
US4634551A (en) * | 1985-06-03 | 1987-01-06 | Procter & Gamble Company | Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain |
US4749516A (en) * | 1985-09-24 | 1988-06-07 | S. C. Johnson & Son, Inc. | Anionic emulsion pre-spotting composition |
CA1283511C (en) * | 1986-09-02 | 1991-04-30 | Colgate-Palmolive | Laundry pre-spotter composition providing improved oily soil removal |
US4915854A (en) * | 1986-11-14 | 1990-04-10 | The Procter & Gamble Company | Ion-pair complex conditioning agent and compositions containing same |
US5002684A (en) * | 1987-04-08 | 1991-03-26 | Harris Research, Inc. | Composition and method for removal of stains from fibers |
US5205960A (en) * | 1987-12-09 | 1993-04-27 | S. C. Johnson & Son, Inc. | Method of making clear, stable prespotter laundry detergent |
US4954286A (en) * | 1988-04-14 | 1990-09-04 | Lever Brothers Company | Fabric pretreatment cleaning compositions |
DE4303454A1 (en) * | 1993-02-05 | 1994-08-11 | Nouvelle Cosmetic Gmbh | Method for removing stains (spots) and stain-removing set |
DE69326757T2 (en) * | 1993-07-12 | 2000-05-31 | Procter & Gamble | Stable, aqueous emulsions of nonionic surfactants with a viscosity control agent |
EP0779357A1 (en) * | 1995-12-16 | 1997-06-18 | The Procter & Gamble Company | Stable emulsions comprising a hydrophobic liquid ingredient |
-
1996
- 1996-09-16 AU AU71098/96A patent/AU7109896A/en not_active Abandoned
- 1996-09-16 WO PCT/US1996/014772 patent/WO1997020095A1/en not_active Application Discontinuation
- 1996-09-16 CA CA002238620A patent/CA2238620C/en not_active Expired - Fee Related
- 1996-09-16 AU AU69783/96A patent/AU6978396A/en not_active Abandoned
- 1996-09-16 WO PCT/US1996/014821 patent/WO1997020098A1/en active Application Filing
- 1996-09-16 MX MX9804177A patent/MX9804177A/en unknown
- 1996-09-16 BR BR9612283A patent/BR9612283A/en not_active Application Discontinuation
- 1996-09-16 DE DE69626311T patent/DE69626311T2/en not_active Expired - Fee Related
- 1996-09-16 AU AU69787/96A patent/AU6978796A/en not_active Abandoned
- 1996-09-16 ES ES96930883T patent/ES2188785T3/en not_active Expired - Lifetime
- 1996-09-16 AT AT96930883T patent/ATE232919T1/en not_active IP Right Cessation
- 1996-09-16 CA CA002238482A patent/CA2238482C/en not_active Expired - Fee Related
- 1996-09-16 JP JP09520456A patent/JP3085986B2/en not_active Expired - Fee Related
- 1996-09-16 BR BR9611791A patent/BR9611791A/en not_active Application Discontinuation
- 1996-09-16 EP EP96930883A patent/EP0871808B1/en not_active Expired - Lifetime
- 1996-09-16 WO PCT/US1996/014766 patent/WO1997020094A1/en active IP Right Grant
- 1996-09-16 EP EP96932226A patent/EP0866893A4/en not_active Withdrawn
- 1996-09-16 JP JP52045797A patent/JP3412111B2/en not_active Expired - Fee Related
- 1996-11-26 EG EG104796A patent/EG20922A/en active
- 1996-11-26 ZA ZA969921A patent/ZA969921B/en unknown
- 1996-11-26 ZA ZA9609925A patent/ZA969925B/en unknown
- 1996-11-27 BR BR9611771A patent/BR9611771A/en not_active Application Discontinuation
- 1996-11-27 AR ARP960105352A patent/AR004771A1/en unknown
- 1996-11-27 AU AU12766/97A patent/AU1276697A/en not_active Abandoned
- 1996-11-27 AR ARP960105354A patent/AR004773A1/en unknown
- 1996-11-27 AT AT96943549T patent/ATE241691T1/en not_active IP Right Cessation
- 1996-11-27 AR ARP960105353A patent/AR004772A1/en unknown
-
1998
- 1998-05-25 NO NO982359A patent/NO982359D0/en not_active Application Discontinuation
- 1998-05-25 NO NO982360A patent/NO982360L/en not_active Application Discontinuation
- 1998-05-26 MX MX9804179A patent/MX9804179A/en not_active Application Discontinuation
- 1998-05-26 MX MX9804178A patent/MX9804178A/en unknown
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