NO171796B - STABLE, LIQUID DETERGENT MIXTURE - Google Patents
STABLE, LIQUID DETERGENT MIXTURE Download PDFInfo
- Publication number
- NO171796B NO171796B NO870366A NO870366A NO171796B NO 171796 B NO171796 B NO 171796B NO 870366 A NO870366 A NO 870366A NO 870366 A NO870366 A NO 870366A NO 171796 B NO171796 B NO 171796B
- Authority
- NO
- Norway
- Prior art keywords
- softening
- mixture
- mixture according
- alkyl
- ethylene oxide
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 60
- 239000003599 detergent Substances 0.000 title claims description 49
- 239000007788 liquid Substances 0.000 title claims description 15
- -1 alkyl glycoside Chemical class 0.000 claims description 43
- 229930182470 glycoside Natural products 0.000 claims description 24
- 239000004744 fabric Substances 0.000 claims description 22
- 239000002736 nonionic surfactant Substances 0.000 claims description 20
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 19
- 239000003945 anionic surfactant Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002338 glycosides Chemical class 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 8
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical group [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 2
- 239000008365 aqueous carrier Substances 0.000 claims 1
- 238000005282 brightening Methods 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 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 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000002979 fabric softener Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- QKIAYRRGJHLRAQ-UHFFFAOYSA-N hexadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 QKIAYRRGJHLRAQ-UHFFFAOYSA-N 0.000 description 2
- 230000003165 hydrotropic effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920002257 Plurafac® Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- XDRMBCMMABGNMM-UHFFFAOYSA-N ethyl benzenesulfonate Chemical compound CCOS(=O)(=O)C1=CC=CC=C1 XDRMBCMMABGNMM-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 description 1
- SSILHZFTFWOUJR-UHFFFAOYSA-N hexadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCS(O)(=O)=O SSILHZFTFWOUJR-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 238000010412 laundry washing Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- TWBKZBJAVASNII-UHFFFAOYSA-N pentadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCS(O)(=O)=O TWBKZBJAVASNII-UHFFFAOYSA-N 0.000 description 1
- CAOVKIWLIMUXEU-UHFFFAOYSA-N pentadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 CAOVKIWLIMUXEU-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- BGHJOVPDUCMEAT-UHFFFAOYSA-M potassium;phenylmethanesulfonate Chemical class [K+].[O-]S(=O)(=O)CC1=CC=CC=C1 BGHJOVPDUCMEAT-UHFFFAOYSA-M 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 229940048842 sodium xylenesulfonate Drugs 0.000 description 1
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 description 1
- RLJSXMVTLMHXJS-UHFFFAOYSA-M sodium;4-decylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 RLJSXMVTLMHXJS-UHFFFAOYSA-M 0.000 description 1
- XZTJQQLJJCXOLP-UHFFFAOYSA-M sodium;decyl sulfate Chemical compound [Na+].CCCCCCCCCCOS([O-])(=O)=O XZTJQQLJJCXOLP-UHFFFAOYSA-M 0.000 description 1
- HHURSJAUVYNJBT-UHFFFAOYSA-M sodium;heptadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCOS([O-])(=O)=O HHURSJAUVYNJBT-UHFFFAOYSA-M 0.000 description 1
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 description 1
- NWZBFJYXRGSRGD-UHFFFAOYSA-M sodium;octadecyl sulfate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCOS([O-])(=O)=O NWZBFJYXRGSRGD-UHFFFAOYSA-M 0.000 description 1
- ORLPWCUCEDVJNN-UHFFFAOYSA-N sodium;tetradecyl benzenesulfonate Chemical compound [Na].CCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 ORLPWCUCEDVJNN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- MYOWBHNETUSQPA-UHFFFAOYSA-N tetradecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCS(O)(=O)=O MYOWBHNETUSQPA-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- GTSMGKYOGFOSAR-UHFFFAOYSA-N tridecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCS(O)(=O)=O GTSMGKYOGFOSAR-UHFFFAOYSA-N 0.000 description 1
- UWSCPROMPSAQOL-UHFFFAOYSA-N trimethylazanium;sulfate Chemical compound CN(C)C.CN(C)C.OS(O)(=O)=O UWSCPROMPSAQOL-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0084—Antioxidants; Free-radical scavengers
-
- 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
- C11D1/662—Carbohydrates or derivatives
-
- 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
- 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
- C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Biochemistry (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Foreliggende oppfinnelse vedrører en stabil, flytende vaskemiddelblanding som er fri for myknende, kvaternære ammoniumforbindelser, hvor blandingen har tøymyknende egenskaper og forbedret rengjøringskraft i fravær av de myknende, kationiske, kvaternære ammoniumforbindelser. The present invention relates to a stable, liquid detergent mixture which is free of softening, quaternary ammonium compounds, where the mixture has fabric softening properties and improved cleaning power in the absence of the softening, cationic, quaternary ammonium compounds.
Bruken av forskjellige og uensartede kjemiske stoffer og særlig kationiske kvaternære ammoniumforbindelser som myknere for tekstilprodukter er svært godt kjent innen teknikken. Det er også godt kjent å anvende slike stoffer på grunn av deres mykningsvirkninger under vaskingen og særlig i skylleperioden i vaskeprosessen. Denne sistnevnte teknikk er blitt nødvendiggjort på grunn av det faktum at de tidligere nevnte kvaternære forbindelser som hittil har vært brukt, og som hovedsakelig er kationiske av natur, ikke er forenlige med de anioniske vaskemidler, en av hovedvaske-middeltypene som brukes i vaskeperioden. Videre er kationiske kvaternære forbindelser forholdsvis ineffektive i nærvær av ikke-ioniske vaskemidler. The use of various and non-uniform chemical substances and in particular cationic quaternary ammonium compounds as plasticizers for textile products is very well known in the art. It is also well known to use such substances because of their softening effects during washing and especially during the rinsing period in the washing process. This latter technique has been necessitated by the fact that the aforementioned quaternary compounds hitherto used, which are mainly cationic in nature, are not compatible with the anionic detergents, one of the main types of detergents used in the wash cycle. Furthermore, cationic quaternary compounds are relatively ineffective in the presence of non-ionic detergents.
Det er også velkjent at det er en tilbøyelighet for vaskede artikler å gulne eller misfarges når de behandles med de nevnte kvaternære forbindelser. It is also well known that there is a tendency for washed articles to yellow or discolor when treated with the aforementioned quaternary compounds.
En annen ulempe forbundet med bruken av de kationiske midler ved vaskingen av stoffer er innvirkningen på avset-ningene av optisk hvitemiddel på stoffene, derved reduksjon av den optiske hvitgjøringen til en vaskemiddelblanding som inneholder det optiske hvitemiddel. Another disadvantage associated with the use of the cationic agents when washing fabrics is the effect on the deposits of optical brightener on the fabrics, thereby reducing the optical whitening of a detergent mixture containing the optical brightener.
Nok en annen ulempe ved den antistatisk kationiske kvaternære ammoniummykner er dens innvirkning på rengjørings-egenskapene til vaskemidlet ved at den reduserer smussfjer-ningen som bevirkes av vaskemidlet, noe som resulterer i ned-satt vaskeeffektivitet. Tilstedeværelsen av det anioniske vaskemiddelstoff opphever i vesentlig grad de stoffmyknende egenskaper til de kationiske kvaternære ammoniumforbindelser. Yet another disadvantage of the antistatic cationic quaternary ammonium softener is its effect on the cleaning properties of the detergent in that it reduces the soil removal effected by the detergent, resulting in reduced washing efficiency. The presence of the anionic detergent substance substantially cancels the fabric softening properties of the cationic quaternary ammonium compounds.
Følgelig er de tidligere nevnte kvaternære midler blitt blandet med en rekke forskjellige forbindelser utformet for å motvirke de ugunstige vaskeegenskapene, eller de kvaternære mykningsmidlene er blitt erstattet av andre mykningsmidler for å forsterke rengjøringskraften. Accordingly, the aforementioned quaternary agents have been mixed with a number of different compounds designed to counteract the unfavorable washing properties, or the quaternary softeners have been replaced by other softeners to enhance cleaning power.
Høyerealkylmono- og poly-glykosider som kan brukes som vaskemidler, tekstilmyknere, overflateaktive midler, gel-danningsmidler, emulgeringsmidler for matvarer og smøremidler, samt fremgangsmåter for fremstilling av disse, er blitt beskrevet i US patentskrifter nr. 3 598 865, 3 707 535, 3 839 318, 3 772 269 og 3 219 656. Higher alkyl mono- and poly-glycosides which can be used as detergents, fabric softeners, surface-active agents, gel-forming agents, emulsifiers for foodstuffs and lubricants, as well as methods for their production, have been described in US patent documents no. 3,598,865, 3,707,535, 3,839,318, 3,772,269 and 3,219,656.
Høyerealkylpolyglykosider er blitt brukt som ikke-ioniske overflateaktive midler i en rekke vaskemiddelblandinger sammen med anioniske overflateaktive midler, slik som vist i US patentskrifter nr. 3 721 633 og 4 483 787, og i europeiske patentskrifter nr. 70.074, 70.075, 70.076 og 92.877. Higher alkyl polyglycosides have been used as nonionic surfactants in a variety of detergent compositions together with anionic surfactants, as shown in US Patent Nos. 3,721,633 and 4,483,787, and in European Patent Nos. 70,074, 70,075, 70,076 and 92,877.
De høyerealkylpolyglykosider er også blitt brukt for The higher alkyl polyglycosides have also been used for
å forbedre vaskeeffekten av ikke-ioniske overflateaktive midler i tøyvaskeblandinger, slik som vist i US patentskrift nr. 4 483 779 og i europeiske patentskrifter nr. 75.994, to improve the washing effect of non-ionic surfactants in laundry detergent compositions, as shown in US Patent No. 4,483,779 and in European Patent No. 75,994,
75.995 og 75.996. 75,995 and 75,996.
Innen den tidligere kjente teknikk er det også beskrevet vaskemiddelblandinger som inneholder et alkylpolyglykosid, et konvensjonelt ikke-ionisk overflateaktivt middel og en kationisk tøymyknende forbindelse, for å gi egenskaper både med hensyn til mykning og vaskevirkning under tøyvasking, slik som vist i US patentskrift nr. 4 493 773 og i europeiske patentskrifter nr. 94.118 og 106.692. Ifølge disse patentskriftene unngåes imidlertid utrykkelig anioniske overflateaktive midler ettersom de er skadelige for blandingen. Within the prior art, detergent mixtures containing an alkyl polyglycoside, a conventional non-ionic surfactant and a cationic fabric softening compound have also been described, to provide properties both with respect to softening and washing action during laundry washing, as shown in US patent document no. 4,493,773 and in European Patent Nos. 94,118 and 106,692. According to these patents, however, anionic surfactants are expressly avoided as they are harmful to the mixture.
Europeisk patentskrift nr. 15.556 beskriver et flytende oppvaskmiddel som gir hurtig og forholdsvis fullstendig av-renning av skyllevann for å redusere flekking og filmdannelse på slike overflater som glass, keramikk og metall, og som omfatter en stor andel anionisk overflateaktivt middel og mindre mengder høyerealkylpolyglykosid og ikke-ionisk overflateaktivt middel. European patent document no. 15,556 describes a liquid washing-up agent which provides rapid and relatively complete run-off of rinse water to reduce staining and film formation on such surfaces as glass, ceramics and metal, and which comprises a large proportion of anionic surfactant and smaller amounts of higher alkyl polyglycoside and nonionic surfactant.
I US patentskrift nr. 4 488 981 beskrives bruken av US Patent No. 4,488,981 describes the use of
1 - 10% C2-Cg-alkylglykosider som et hydrotropt middel, dvs. 1 - 10% C2-C8 alkylglycosides as a hydrotropic agent, i.e.
for å redusere viskositet og forhindre faseseparasjon, i vaskemiddelblandinger som inneholder ikke-ioniske og/eller to reduce viscosity and prevent phase separation, in detergent mixtures containing non-ionic and/or
anioniske og/eller kationiske overflateaktive midler. anionic and/or cationic surfactants.
Imidlertid beskrives det ikke i noen av litteratur-referansene en flytende blanding av mykningsmiddel og vaskemiddel for samtidig rengjøring og mykning av stoffer som omfatter tre vesentlige bestanddeler, en effektiv myknende mengde av et alkylglykosid som også forbedrer vaskeegenskaper og et overflateaktivt system bestående hovedsakelig av en stor mengde av et ikke-ionisk overflateaktivt middel og en mindre mengde av et anionisk overflateaktivt middel. However, none of the literature references describe a liquid mixture of softener and detergent for the simultaneous cleaning and softening of substances comprising three essential components, an effective softening amount of an alkyl glycoside which also improves washing properties and a surface-active system consisting mainly of a large amount of a nonionic surfactant and a smaller amount of an anionic surfactant.
Det er nå oppdaget at tilsetningen av et overflateaktivt alkylpolyglykosid til en stabil flytende vaskemiddelblanding gir stoffmyknende egenskaper i fravær av alle andre kjente mykningsmidler, og forsterker vaskeeffekten til en blanding av ikke-ionisk og anionisk overflateaktivt middel. It has now been discovered that the addition of a surfactant alkyl polyglycoside to a stable liquid detergent mixture provides fabric softening properties in the absence of all other known softeners, and enhances the washing effect of a mixture of nonionic and anionic surfactants.
Følgelig er det et hovedformål ved foreliggende oppfinnelse å tilveiebringe en flytende vaskemiddelblanding med tøymyknende egenskaper og forbedret rengjøringsstyrke i fravær av myknende kationiske kvaternære ammoniumforbindelser. Accordingly, it is a main object of the present invention to provide a liquid detergent mixture with fabric softening properties and improved cleaning power in the absence of softening cationic quaternary ammonium compounds.
Et annet formål ved oppfinnelsen er å tilveiebringe Another object of the invention is to provide
en flytende vaskemiddelblanding som samtidig renser og mykner stoffer under vaskeprosessen, og som omfatter et alkylglykosid, et ikke-ionisk overflateaktivt middel og et anionisk overflateaktivt middel som de tre vesentlige bestanddeler. a liquid detergent mixture that simultaneously cleans and softens substances during the washing process, and which comprises an alkyl glycoside, a non-ionic surfactant and an anionic surfactant as the three essential components.
Nok et annet formål ved oppfinnelsen er å tilveiebringe en flytende vaskemiddelblanding med forbedrede rengjørings- Yet another object of the invention is to provide a liquid detergent mixture with improved cleaning
og mykningsegenskaper på grunn av tilstedeværelsen av et alkylglykosid i en vaskemiddelblanding som inneholder en blanding av ikke-ioniske og anioniske overflateaktive midler. and softening properties due to the presence of an alkyl glycoside in a detergent composition containing a mixture of nonionic and anionic surfactants.
Ytterligere formål, fordeler og nye trekk ved oppfinnelsen vil delvis fremgå av beskrivelsen som følger nedenunder, og vil delvis åpenbares for fagfolk innen teknikken etter gjennomgåelse av det som følger nedenunder, eller.kan læres ved utøvelse av oppfinnelsen. Formålene og fordelene ifølge oppfinnelsen kan realiseres og oppnåes ved hjelp av de trekkene og kombinasjonene som er angitt i kravene. Further objects, advantages and new features of the invention will be apparent in part from the description that follows, and will in part be revealed to those skilled in the art after reviewing what follows below, or can be learned by practicing the invention. The purposes and advantages according to the invention can be realized and achieved with the help of the features and combinations indicated in the claims.
I henhold til foreliggende oppfinnelse er det således tilveiebrakt en stabil, flytende vaskemiddelblanding som er fri for myknende, kvaternære ammoniumforbindelser, hvor blandingen har tøymyknende egenskaper og forbedret rengjøringskraft i fravær av de myknende, kationiske, kvaternære ammoniumforbindelser. Vaskemiddelblandingen ifølge oppfinnelsen er kjennetegnet ved at den består hovedsakelig av et tøymyknende alkylglykosid med en eller flere hydrofobe kjeder valgt fra gruppen bestående av methyl og C8_23-alkyl og inneholdende 1-10 saccharidradikaler i en tøymyknende mengde på 6-30 vekt%, 15-30 vekt% ikke-ionisk, overflateaktivt middel som inneholder hydrofile ethylenoksydgrupper, og 4-12 vekt% av et vannopp-løselig, anionisk, overflateaktivt salt valgt fra gruppen bestående av C10-C18-alkylbenzensulfonater, C10-C22-<a>lkylsulfo-nater, <C>10-C20-alkylsulfater, C10-C20-alkylethoxysulfater og C12-C18-olefinsulfonater, idet mengden av det anioniske, overflateaktive middel er mindre enn 50 vekt% av det ikke-ioniske, overflateaktive middel, i en vandig bærer. According to the present invention, a stable, liquid detergent mixture is thus provided which is free of softening, quaternary ammonium compounds, where the mixture has fabric softening properties and improved cleaning power in the absence of the softening, cationic, quaternary ammonium compounds. The detergent mixture according to the invention is characterized in that it consists mainly of a fabric softening alkyl glycoside with one or more hydrophobic chains selected from the group consisting of methyl and C8_23-alkyl and containing 1-10 saccharide radicals in a fabric softening amount of 6-30% by weight, 15-30 % by weight of nonionic surfactant containing hydrophilic ethylene oxide groups, and 4-12% by weight of a water-soluble anionic surfactant salt selected from the group consisting of C10-C18-alkylbenzenesulfonates, C10-C22-<a>alkylsulfonates .
Alkylglykosidene virker som stoffmyknende midler like-såvel som de forsterker vaskeeffekten i en blanding av ikke-ionisk og anionisk overflateaktivt middel. Det antas at alkylglykosidene tildekker overflaten på stoffet og/eller endrer stoffstrukturen og derved gir fordeler med hensyn til mykning. Det antas at alkylglykosidene kan bryte hydrogen-binding og derved gjøre blandingen mer tilgjengelig for stoffer enn de myknende kvaternære ammoniumforbindelser, slik at stoffene tilføres utmerkede mykningsegenskaper i fravær av kvaternære mykningsmidler. Alkylglykosidene virker ikke inn på vaskeeffekten og/eller avsetningen av hvitemiddel som er et vanlig problem ved blandinger av myknings- og vaskemidler. Det oppstår ingen problemer med hensyn til fettflekking og vannimpregnering. The alkyl glycosides act as fabric softeners as well as enhancing the washing effect in a mixture of non-ionic and anionic surfactants. It is believed that the alkyl glycosides cover the surface of the fabric and/or change the fabric structure and thereby provide benefits in terms of softening. It is believed that the alkyl glycosides can break hydrogen bonds and thereby make the mixture more accessible to substances than the softening quaternary ammonium compounds, so that the substances are given excellent softening properties in the absence of quaternary softeners. The alkyl glycosides do not affect the washing effect and/or the deposition of bleach, which is a common problem with mixtures of softeners and detergents. No problems arise with regard to grease staining and water impregnation.
Alkylglykosidene som benyttes i foreliggende nye.blanding av myknings- og vaskemiddel, defineres ved at de har én eller flere hydrofobe kjeder valg fra gruppen bestående av methyl og C8.23-alkyl og inneholder 1-10, og fortrinnsvis 1-3, saccharidradikaler. Den hydrofobe kjede kan være mettet eller umettet, forgrenet eller rettkjedet, fortrinnsvis mettet og rettkjedet, når den inneholder 8-23 carbonatomer. Egnedealkylpolyglyko-sider omfatter methyl-, octyl-, nonyl-, decyl-, undecyl-, dodecyl-, tridecyl-, tetradecyl-, hexadexyl-, heptadecyl-, octadecyl-, og blandinger derav, -monoglykosider, -diglyko-sider, -triglykosider, -tetraglykosider, -pentaglykosider, -hexaglykosider, etc. Glykosidenhetene kan være glukose, galaktose, mannose, laktose og/eller fruktose. Fremgangsmåter for fremstilling av de nevnte glykosider er beskrevet i US patentskrifter nr. 3 598 865, 3 707 535, 3 839 318, 3 772 269 og 3 219 656. Tilsetningen av alkylglykosidet til vaskemidlet gir tøymyknende egenskaper samt forbedrer rengjøringsstyrken. Glykosidmengden må være tilstrekkelig til å mykne stoffer i fravær av kjente mykningsmidler, slik som de kationiske kvaternære ammonium-mykningsmidler, og utgjør minst 6 vekt% og opp til 30 vekt% av blandingen. The alkyl glycosides used in the present new mixture of softener and detergent are defined in that they have one or more hydrophobic chains selected from the group consisting of methyl and C8.23-alkyl and contain 1-10, and preferably 1-3, saccharide radicals. The hydrophobic chain can be saturated or unsaturated, branched or straight chain, preferably saturated and straight chain, when it contains 8-23 carbon atoms. Suitable alkylpolyglycosides include methyl-, octyl-, nonyl-, decyl-, undecyl-, dodecyl-, tridecyl-, tetradecyl-, hexadecyl-, heptadecyl-, octadecyl-, and mixtures thereof, -monoglycosides, -diglycosides, - triglycosides, -tetraglycosides, -pentaglycosides, -hexaglycosides, etc. The glycoside units can be glucose, galactose, mannose, lactose and/or fructose. Methods for producing the aforementioned glycosides are described in US patent documents no. 3 598 865, 3 707 535, 3 839 318, 3 772 269 and 3 219 656. The addition of the alkyl glycoside to the detergent provides fabric softening properties and improves cleaning power. The amount of glycoside must be sufficient to soften substances in the absence of known softeners, such as the cationic quaternary ammonium softeners, and constitutes at least 6% by weight and up to 30% by weight of the mixture.
Det ble utført en 3-perioders "clean-load" mykningstest under anvendelse av glukose med en C^2~C13 <c>ark°nkjede festet til det anomere carbonatom (APG-23-1). De anvendte kontroller var "Solo"=10 og "DAP"=1. i testen ble det tatt med en annen blanding hvor det ble brukt et monotalg-trimethylammoniumsulfat. A 3-period "clean-load" softening test was performed using glucose with a C2~C13 sheet chain attached to the anomeric carbon atom (APG-23-1). The controls used were "Solo"=10 and "DAP"=1. in the test, a different mixture was used where a monotallow trimethylammonium sulfate was used.
("M Quat 620"). Alle mykningsmidler ble tilsatt i en mengde på 6%. Fem paneldeltagere evaluerte produktene. ("M Quat 620"). All softeners were added in an amount of 6%. Five panelists evaluated the products.
1. vaskeperiode 1st washing period
Den uventede overlegenhet til alkylglykosidet som et mykningsmiddel, i forhold til den tidligere kjente kvaternære mykner som ble påvist ovenfor, overvinner de iboende problemer som er forbundet med bruken av de kvaternære forbindelser i vaskemiddelblandinger. Det er nå mulig å formulere en blanding hvor hverken vaskevirkning eller mykningsvirkning kompromit-teres . The unexpected superiority of the alkyl glycoside as a softener over the prior art quaternary softener demonstrated above overcomes the inherent problems associated with the use of the quaternary compounds in detergent compositions. It is now possible to formulate a mixture where neither the washing effect nor the softening effect is compromised.
De ikke-ioniske overflateaktive midler for bruk som stoffvaskemidler ifølge foreliggende oppfinnelse er kommersielt velkjente og omfatter ethoxylater av primære alifatiske alkoholer, ethoxylater av sekundære alifatiske alkoholer, ethoxylater av alkylfenol og slike kondensater av alkoholer og ethylenoxyd/propylenoxyd som Plurafac<®->produktene (Wyan-dotte), samt blandinger derav. De ikke-ioniske syntetiske organiske vaskemidler er vanligvis kondensasjonsprodukter av en organisk alifatisk eller alkylaromatisk hydrofob forbindelse og hydrofile ethylenoxydgrupper. Praktisk talt hvilken som helst hydrofob forbindelse med en carboxyl-, hydroxyl-, amid-eller aminogruppe med et fritt hydrogenatom bundet til nitro-genatomet kan kondenseres med ethylenoxyd eller med poly-hydratiseringsproduktet derav, polyethylenglycol, hvorved det dannes et ikke-ionisk vaskemiddel. Videre kan lengden av poly-ethenoxykjeden reguleres for å oppnå den ønskede likevekt mellom de hydrofobe og hydrofile elementer. The non-ionic surfactants for use as fabric detergents according to the present invention are commercially well known and include ethoxylates of primary aliphatic alcohols, ethoxylates of secondary aliphatic alcohols, ethoxylates of alkylphenol and such condensates of alcohols and ethylene oxide/propylene oxide as the Plurafac<®> products ( Wyan-dotte), as well as mixtures thereof. The nonionic synthetic organic detergents are usually condensation products of an organic aliphatic or alkylaromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound with a carboxyl, hydroxyl, amide or amino group with a free hydrogen atom attached to the nitrogen atom can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, thereby forming a nonionic detergent. Furthermore, the length of the poly-ethenoxy chain can be regulated to achieve the desired equilibrium between the hydrophobic and hydrophilic elements.
De ikke-ioniske vaskemidler omfatter polyethylenoxyd-kondensatet av 1 mol alkylfenol som inneholder fra 6 til 12 carbonatomer i en rettkjedet eller forgrenet konfigurasjon, med 5 til 30 mol ethylenoxyd, f.eks. nonylfenol kondensert med 9 mol ethylenoxyd, dodecylfenol kondensert med 15 mol ethylenoxyd. Kondensasjonsprodukter av tilsvarende alkylthio-fenoler med 5-30 mol ethylenoxyd er også egnet. The nonionic detergents comprise the polyethylene oxide condensate of 1 mole of alkylphenol containing from 6 to 12 carbon atoms in a straight chain or branched configuration, with 5 to 30 moles of ethylene oxide, e.g. nonylphenol condensed with 9 mol ethylene oxide, dodecylphenol condensed with 15 mol ethylene oxide. Condensation products of corresponding alkylthiophenols with 5-30 mol ethylene oxide are also suitable.
Inkludert i klassen av ikke-ioniske vaskemidler er Included in the class of non-ionic detergents are
også kondensasjonsproduktene av en høyere alkohol (f.eks. en alkanol med 8' - 18 carbonatomer i en rettkjedet eller forgrenet konfigurasjon) kondensert med 5-30 mol ethylenoxyd, f.eks. lauryl-myristyl-alkohol kondensert med ca. 16 mol ethylenoxyd. also the condensation products of a higher alcohol (e.g. an alkanol with 8'-18 carbon atoms in a straight-chain or branched configuration) condensed with 5-30 moles of ethylene oxide, e.g. lauryl-myristyl alcohol condensed with approx. 16 moles of ethylene oxide.
En foretrukket gruppe ikke-ioniske overflateaktive midler er "Neodol"-ethoxylåtene (Shell Co.) som er høyere alifatiske alkoholethoxylater med ca. 5 til 20 ethylenoxydgrupper pr. mol alifatisk alkohol som inneholder ca. 10 - 18 carbonatomer, slik somC^-C^ alkanol kondensert med 6,5 mol ethylenoxyd, C^_ 2~ C15 alkanol kondensert med 12 mol ethylenoxyd, <C>1^-C^5 alkanol kondensert med 13 mol ethylenoxyd og lignende. Ethoxamerer med en HLB (hydrofob/lipofil likevekt)-verdi på A preferred group of nonionic surfactants are the "Neodol" ethoxylates (Shell Co.) which are higher aliphatic alcohol ethoxylates with approx. 5 to 20 ethylene oxide groups per moles of aliphatic alcohol containing approx. 10 - 18 carbon atoms, such as C^-C^ alkanol condensed with 6.5 mol ethylene oxide, C^_ 2~ C15 alkanol condensed with 12 mol ethylene oxide, <C>1^-C^5 alkanol condensed with 13 mol ethylene oxide and the like . Ethoxamers with an HLB (hydrophobic/lipophilic balance) value of
ca. 8-15 gir god olje/vann-emulgering, mens ethoxamerer med lave HLB-verdier (under 8) inneholder mindre enn 5 ethylenoxydgrupper, og er dårlige emulgeringsmidler og dårlige ikke-ioniske vaskemidler. Dette ikke-ioniske overflateaktive middel er til stede i vaskemiddelblandingen i en mengde som er minst dobbelt så stor som innholdet av det anioniske overflateaktive middel, og utgjør 15-30 vekt%. Det ikke-ioniske overflate- about. 8-15 give good oil/water emulsification, while ethoxamers with low HLB values (below 8) contain less than 5 ethylene oxide groups, and are poor emulsifiers and poor non-ionic detergents. This nonionic surfactant is present in the detergent mixture in an amount that is at least twice the content of the anionic surfactant, and amounts to 15-30% by weight. The non-ionic surface-
aktive middel, dvs. de ikke-ioniske alkoholethoxylater definert ovenfor, utgjør den største vaskemiddelbestanddel i denne blanding. active agent, i.e. the nonionic alcohol ethoxylates defined above, constitute the largest detergent component in this mixture.
De anioniske overflateaktive midler som benyttes i vaskemidlet ifølge oppfinnelsen, er kommersielt velkjente og omfatter C10-C18-alkylbenzensulfonater, f.eks. forbindelser med formelen alkyl-fenyl-S03-N, hvor alkyl er et alkylradikal med C10-C18, og M er et alkalimetall, idet forbindelsene omfatter en velkjent klasse anioniske vaskemidler og omfatter natrium-dodecylbenzensulfonat, kaliumdodecylbenzensulfonat, natrium-laurylbenzensulfonat og natriumcetylbenzensulfonat. The anionic surfactants used in the detergent according to the invention are commercially well known and comprise C10-C18 alkylbenzene sulphonates, e.g. compounds of the formula alkyl-phenyl-SO3-N, where alkyl is an alkyl radical with C10-C18, and M is an alkali metal, the compounds comprising a well-known class of anionic detergents and comprising sodium dodecylbenzenesulfonate, potassium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate and sodium cetylbenzenesulfonate.
Andre omfatter C10-C22-alkylsulfonater, C10-<C>20-alkylsulfater, C10-C20-<a>lkylethoxysulfater og C12-C18-olefinsulfonater. Others include C10-C22 alkyl sulfonates, C10-<C>20 alkyl sulfates, C10-C20-<a>alkyl ethoxy sulfates and C12-C18 olefin sulfonates.
Blant de ovenfor angitte alkylbenzensulfonater omfatter de foretrukne forbindelser de som er biologisk nedbryt-bare og som er spesielt kjennetegnet ved en rettkjedet alkyl-substituent med fra C10-C18, og fortrinnsvis fra C12 til C15. Det skal imidlertid forståes at carbonkjedelengden vanligvis representerer en gjennomsnittlig kjedelengde ettersom det ved fremgangsmåten for fremstilling av slike produkter vanligvis anvendes alkyleringsreagenser med blandet kjedelengde. Det er imidlertid klart at i det vesentlige rene olefiner samt alkyleringsforbindelser som brukes i andre teknikker, kan gi og gir alkylerte benzensulfonater hvor alkylresten hovedsakelig (dvs. minst 99 %) er av én kjedelengde, dvs. C12, C13, C14 og C15. De rettkjedede alkylbenzensulf onater er videre kjennetegnet ved stillingen til benzenringen i den rettkjedede alkylrest, idet alle stillingsisomerene (dvs. a til o) kan brukes og er omfattet. Among the above-mentioned alkylbenzenesulfonates, the preferred compounds include those which are biodegradable and which are particularly characterized by a straight-chain alkyl substituent with from C10-C18, and preferably from C12 to C15. However, it should be understood that the carbon chain length usually represents an average chain length, as alkylation reagents with mixed chain lengths are usually used in the process for producing such products. However, it is clear that substantially pure olefins as well as alkylating compounds used in other techniques can and do yield alkylated benzene sulfonates where the alkyl residue is predominantly (ie at least 99%) of one chain length, ie C12, C13, C14 and C15. The straight-chain alkylbenzene sulfonates are further characterized by the position of the benzene ring in the straight-chain alkyl residue, since all positional isomers (ie a to o) can be used and are covered.
Eksempler på egnede rettkjedede alkylbenzensulfonater omfatter: natrium-decylbenzensulfonat Examples of suitable straight chain alkylbenzenesulfonates include: sodium decylbenzenesulfonate
natrium-dodecylbenzensulfonat sodium dodecylbenzene sulfonate
natrium-tetradecylbenzensulfonat sodium tetradecylbenzenesulfonate
natrium-n-pentadecylbenzensulfonat sodium n-pentadecylbenzenesulfonate
natrium-n-hexadecylbenzensulfonat sodium n-hexadecylbenzenesulfonate
samt saltene av de kationene som det tidligere er henvist til. Blandinger av disse sulfonater kan selvfølgelig også brukes med blandinger som kan omfatte forbindelser hvor den as well as the salts of the cations previously referred to. Mixtures of these sulphonates can of course also be used with mixtures which may include compounds where the
rettkjedede alkylrest er mindre eller større enn det som her er angitt,forutsatt at den gjennomsnittlige kjedelengde i blandingen er i overensstemmelse med de bestemte krav på cio~C18*straight-chain alkyl residues are smaller or larger than what is stated here, provided that the average chain length in the mixture is in accordance with the specific requirements for cio~C18*
De rettkjedede alkansulfonater er også en velkjent gruppe forbindelser og omfatter vannoppløselige salter (alkalimetall, amin, alkanolamin og ammonium) av: The straight-chain alkanesulfonates are also a well-known group of compounds and include water-soluble salts (alkali metal, amine, alkanolamine and ammonium) of:
1-decansulfonsyre 1-decanesulfonic acid
1-dodecansulfonsyre 1-dodecanesulfonic acid
1-tridecansulfonsyre 1-tridecanesulfonic acid
1-tetradecansulfonsyre 1-tetradecanesulfonic acid
1-pentadecansulfonsyre 1-pentadecanesulfonic acid
1-hexadecansulfonsyre 1-hexadecanesulfonic acid
samt de øvrige stillingsisomerer av sulfonsyregruppen. as well as the other positional isomers of the sulfonic acid group.
I tillegg til alkansulfonatene som er illustrert ovenfor, kan det brukes andre med det generelle område på ciø~C22 alkylrester, idet det mest foretrukkede område er fra C^2 til In addition to the alkanesulfonates illustrated above, others having a general range of C10~C22 alkyl residues may be used, the most preferred range being from C12 to
rr
<u>20' <u>20'
De rettkjedede alkylsulfater som det er tenkt på i foreliggende oppfinnelse, omfatter området ^ 2. 0~^ 20' Bestemte eksempler omfatter natrium-n-decylsulfat, natrium-n-dodecyl-sulfat, natrium-n-hexadecylsulfat, natrium-n-heptadecylsulfat, natrium-n-octadecylsulfat og de ethoxylerte (1 - 100 mol ethylenoxyd) derivater, slik som de ethoxylerte alkoholsulfater og selvfølgelig de øvrige vannoppløselige saltdannende kationer som er nevnt ovenfor. The straight-chain alkyl sulfates contemplated in the present invention comprise the range ^ 2. 0~^ 20' Certain examples include sodium n-decyl sulfate, sodium n-dodecyl sulfate, sodium n-hexadecyl sulfate, sodium n-heptadecyl sulfate , sodium n-octadecyl sulfate and the ethoxylated (1 - 100 mol ethylene oxide) derivatives, such as the ethoxylated alcohol sulfates and of course the other water-soluble salt-forming cations mentioned above.
Inkludert i gruppen av anioniske vaskemidler som er blitt beskrevet ovenfor som egnet i foreliggende oppfinnelse, er olefinsulfonatene, inkludert langkjedede alkensulfonater, langkjedede hydroxyalkansulfonater, samt disulfonater. Eksempler på egnede olefinsulfonater, som kun er illustrerende for den generelle klasse, er natrium-dodecenyl-l-sulfonat, natrium-tetradecenyl-l-sulfonat, natrium-hexadecenyl-l-sulfonat og natrium-octadecenyl-l-sulfonat. Mengden av anionisk overflateaktivt middel som benyttes i foreliggende blandinger er som nevnt mindre enn vektinnholdet av det ikke-ioniske (ethoxylert alifatisk alkohol) overflateaktive midler, og nærmere bestemt mindre enn 50 vekt% av innholdet av ikke-ionisk overflateaktivt middel, og utgjør 4-12 vekt% av blandingen. Included in the group of anionic detergents that have been described above as suitable in the present invention are the olefin sulfonates, including long-chain alkenesulfonates, long-chain hydroxyalkanesulfonates, as well as disulfonates. Examples of suitable olefin sulfonates, which are only illustrative of the general class, are sodium dodecenyl-1-sulfonate, sodium tetradecenyl-1-sulfonate, sodium hexadecenyl-1-sulfonate and sodium octadecenyl-1-sulfonate. The amount of anionic surfactant used in the present mixtures is, as mentioned, less than the weight content of the non-ionic (ethoxylated aliphatic alcohol) surfactant, and more precisely less than 50% by weight of the content of non-ionic surfactant, and amounts to 4- 12% by weight of the mixture.
Vaskemiddelblandingen ifølge foreliggende oppfinnelse kan også omfatte konvensjonelle vaskemiddeladditiver, slik som optiske hvitemidler, germicider, smussoppslemmende midler, anti-redeponeringsmidler, antioxydanter, fargende materialer (fargestoffer og pigmenter), parfymer, vannoppløselige alkoholer, skumforsterkere, hydrotrope midler, slik som natrium-og kaliumxylensulfonater, natrium- og kaliumtoluensulfonater, cumensulfonater, ethylbenzensulfonat og lignende, enzymer og enzymstabilisatorer, og byggere, slik som tripolyfosfat, bi-carbonat, etc., forutsatt at de ikke virker inn på vaske-ef fekten og mykningsaktiviteten til blandingen. The detergent mixture according to the present invention can also include conventional detergent additives, such as optical brighteners, germicides, dirt-relieving agents, anti-redeposition agents, antioxidants, coloring materials (dyes and pigments), perfumes, water-soluble alcohols, foam boosters, hydrotropic agents, such as sodium and potassium xylene sulfonates , sodium and potassium toluenesulfonates, cumenesulfonates, ethylbenzenesulfonate and the like, enzymes and enzyme stabilizers, and builders, such as tripolyphosphate, bicarbonate, etc., provided they do not affect the washing effect and softening activity of the mixture.
Oppfinnelsen illustreres nærmere ved hjelp av følgende eksempler. The invention is illustrated in more detail by means of the following examples.
Eksempel 1 Example 1
Det flytende vaskemiddel fremstilles ved å blande de ovenfor nevnte bestanddeler inntil blandingen er homogen, hvorved det dannes en stabil flytende blanding. The liquid detergent is prepared by mixing the above-mentioned ingredients until the mixture is homogeneous, whereby a stable liquid mixture is formed.
Eksempel 2 Example 2
Vaskemiddel Detergent
21% "Neodol 25-7" 21% "Neodol 25-7"
4% natrium-dodecylbenzensulfonat 4% sodium dodecylbenzenesulfonate
6% methylglykosid 6% methylglycoside
0,4% hvitemiddel 0.4% bleach
8% ethanol 8% ethanol
5% natrium-xylensulfonat 5% sodium xylene sulfonate
0,5% fargestoff 0.5% dye
Q.S. vann Q.S. water
Denne blandingen ble testet i en 5 perioders, 2,7 kg This mixture was tested in a 5 period, 2.7 kg
"clean load" mykhetstest under anvendelse av "Solo" som kon-trollen med størst mykhetsgrad (10). Mykhetsbedømmelsen for denne blanding, som er 7,2 (gjennomsnittet av disse avles- "clean load" softness test using "Solo" as the control with the greatest degree of softness (10). The softness rating for this blend, which is 7.2 (the average of these read-
ningene etter 1., 2. og 5. periode), holder fint mål med "Solo" som vist i tabell I. Mykhetsbedømmelsen ligger innenfor et område på 1 (det hardeste) til 10 (det mykeste). Fraværet av glykosidet i produktene 1 og 2 som inneholder et kvater- nings after the 1st, 2nd and 5th period), measures up nicely with "Solo" as shown in Table I. The softness rating lies within a range of 1 (the hardest) to 10 (the softest). The absence of the glycoside in products 1 and 2 containing a quaternary
nært mykningsmiddel, gir en blanding med dårligere mykningsegenskaper (henholdsvis 5,9 og 5,8). Den forente bruk av de kvaternære mykningsmidler og glykosidet gir forbedrede mykhets-bedømmelser på 6 og 6,8 (produktene 3 og 4). Utmerkede mykningsegenskaper bevirkes imidlertid ved alenebruken av alkylglykosidet (produkt 5) i forhold til de konvensjonelle kvaternære mykningsmidler. close to the plasticizer, gives a mixture with poorer plasticizing properties (respectively 5.9 and 5.8). The combined use of the quaternary softeners and the glycoside gives improved softness ratings of 6 and 6.8 (products 3 and 4). However, excellent softening properties are achieved by the sole use of the alkyl glycoside (product 5) compared to the conventional quaternary softeners.
Følgende tabell I oppsummerer resultatene for hvit- The following Table I summarizes the results for white-
gjøring og statisk elektrisitet i de 5 perioders tester av mykning/statisk elektrisitet/hvitemiddel på 5 testprodukter og 2 kontroller. Fluorescens hos bomullsstykkene avleses som making and static electricity in the 5 period tests of softening/static electricity/whitening agent on 5 test products and 2 controls. Fluorescence in the cotton pieces is read as
et mål for hvitemiddeleffektivitet (Rb). a measure of bleach efficiency (Rb).
Resultatene ovenfor indikerer at methylglykosid gir utmerkede mykningsfordeler til stoffer. Laboratorietestene indikerer også at glykosidet gir utmerkede hvitgjøringsfor-deler i flytende blandinger. Ved fravær av kvaternær forbindelse oppnåes det imidlertid ingen kontroll av statisk elektrisitet. The above results indicate that methylglycoside provides excellent softening benefits to fabrics. The laboratory tests also indicate that the glycoside provides excellent whitening benefits in liquid mixtures. In the absence of a quaternary connection, however, no control of static electricity is achieved.
Vaskemidlene som inneholder en virksom stoffmyknende mengde av et alkylglykosid, er uventet blitt funnet å forbedre vaskevirknings- og mykningsegenskapene til vaskemiddel-blandingene i fravær av konvensjonelle mykningsmidler, slik som kvaternære ammoniumforbindelser. Dette er tidligere vist i tabell I ved produkt 5 som inneholder 6% methylglykosid. Likeledes oppviser produkt 5 en større hvithet etter 1., 3. og 5. vaskeperiode enn produktene 1, 2 og 4. The detergents containing an effective softening amount of an alkyl glycoside have unexpectedly been found to improve the detergency and softening properties of the detergent compositions in the absence of conventional softening agents, such as quaternary ammonium compounds. This has previously been shown in Table I for product 5, which contains 6% methylglycoside. Likewise, product 5 shows a greater whiteness after the 1st, 3rd and 5th washing period than products 1, 2 and 4.
Flytende vaskemidler Liquid detergents
Blandingene ovenfor ble utsatt for en 3-perioders, The above mixtures were subjected to a 3-period,
0,7 kg "clean fabric load"-test for å konstatere mykningsegenskapene til alkylglykosidene under anvendelse av kommersielle 0.7 kg "clean fabric load" test to ascertain the softening properties of the alkyl glycosides using commercial
produkter "Solo" = 10, som kontroll varierende fra det mykeste (10) til det hardeste (1). Eksempel 8 inneholder et kvaternært ammoniummykningsmiddel i stedet for alkylglykosidet. products "Solo" = 10, as a control varying from the softest (10) to the hardest (1). Example 8 contains a quaternary ammonium softener in place of the alkyl glycoside.
Disse resultatene illustrerer de stoffmyknende egenskaper som oppvises av vaskemiddelblandinger som inneholder alkylglykosider i et ikke-ionisk/anionisk overflateaktivt system hvor det ikke-ioniske overflateaktive middel er hoved-vaskemidlet supplert med mindre mengder anionisk overflateaktivt middel i fravær av kvaternære ammonium-mykningsmidler. These results illustrate the fabric softening properties exhibited by detergent mixtures containing alkyl glycosides in a nonionic/anionic surfactant system where the nonionic surfactant is the main detergent supplemented with smaller amounts of anionic surfactant in the absence of quaternary ammonium softeners.
Så små mengder som 6% alkylglykosid er effektive når det gjelder både vaskevirknings- og mykningsegenskapene til en vaskemiddelblanding som brukes ved vasking av stoffer. Amounts as small as 6% alkyl glycoside are effective in both the detergency and softening properties of a detergent composition used in the washing of fabrics.
I tillegg oppviser foreliggende blandinger bedre rengjørings-og mykningsstyrke enn andre blandinger av overflateaktivt middel og/eller mykner som for tiden er i handelen, slik det fremgår av sammenligningsresultatene i tabell I. In addition, the present compositions exhibit better cleaning and softening power than other surfactant and/or softener compositions currently on the market, as can be seen from the comparative results in Table I.
Claims (7)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US82390686A | 1986-01-30 | 1986-01-30 |
Publications (4)
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NO870366D0 NO870366D0 (en) | 1987-01-29 |
NO870366L NO870366L (en) | 1987-07-31 |
NO171796B true NO171796B (en) | 1993-01-25 |
NO171796C NO171796C (en) | 1993-05-05 |
Family
ID=25240073
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Application Number | Title | Priority Date | Filing Date |
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NO870366A NO171796C (en) | 1986-01-30 | 1987-01-29 | STABLE, LIQUID DETERGENT MIXTURE |
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JP (1) | JPS62197495A (en) |
KR (1) | KR950002352B1 (en) |
AR (1) | AR242258A1 (en) |
AU (1) | AU600694B2 (en) |
BE (1) | BE1001831A5 (en) |
BR (1) | BR8700391A (en) |
CH (1) | CH672138A5 (en) |
DE (1) | DE3702286A1 (en) |
DK (1) | DK51287A (en) |
EG (1) | EG18074A (en) |
ES (1) | ES2004203A6 (en) |
FR (1) | FR2593515B1 (en) |
GB (1) | GB2185991B (en) |
GR (1) | GR870124B (en) |
HK (1) | HK97993A (en) |
IL (1) | IL81354A (en) |
IN (1) | IN169745B (en) |
IT (1) | IT1205727B (en) |
MX (1) | MX168267B (en) |
NL (1) | NL8700230A (en) |
NO (1) | NO171796C (en) |
NZ (1) | NZ219050A (en) |
PH (1) | PH25140A (en) |
SE (1) | SE8700323L (en) |
TR (1) | TR24546A (en) |
ZA (1) | ZA87524B (en) |
ZM (1) | ZM1087A1 (en) |
ZW (1) | ZW1787A1 (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
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IL81353A (en) * | 1986-01-30 | 1990-08-31 | Colgate Palmolive Co | Liquid softergent having improved detergency containing alkyl glycoside |
MY103951A (en) * | 1988-01-12 | 1993-10-30 | Kao Corp | Detergent composition |
US5047165A (en) * | 1989-01-25 | 1991-09-10 | Colgate-Palmolive Co. | Fine fabric laundry detergent with sugar esters as softening and whitening agents |
DE59009494D1 (en) * | 1989-09-26 | 1995-09-14 | Ciba Geigy Ag | Aqueous, storage stable, low foaming wetting agent. |
DE4016819A1 (en) * | 1990-05-25 | 1991-12-19 | Huels Chemische Werke Ag | Low foam liq. or powder machine washing compsn. with surfactant - comprising alkyl-poly:glycoside, alkanol ether carboxylate and soap |
DE4026809A1 (en) * | 1990-08-24 | 1992-02-27 | Henkel Kgaa | Liq. aq. washing compsn. - contains anionic surfactant, nonionic surfactant and alkyl poly:glycoside as thickener, improving washing |
DE59103727D1 (en) * | 1990-08-22 | 1995-01-12 | Henkel Kgaa | LIQUID DETERGENT WITH INCREASED VISCOSITY. |
DE4036662A1 (en) * | 1990-11-17 | 1992-05-21 | Huels Chemische Werke Ag | LIQUID, DELICATE CLEANING AGENT |
DE4116807A1 (en) * | 1991-05-23 | 1992-11-26 | Henkel Kgaa | CONCENTRATED AQUEOUS LIQUID DETERGENT |
DE4338113A1 (en) * | 1993-11-08 | 1995-05-11 | Henkel Kgaa | Softening detergent with alkyl glycosides |
GB9606913D0 (en) | 1996-04-02 | 1996-06-05 | Unilever Plc | Surfactant blends processes for preparing them and particulate detergent compositions containing them |
DE19629667A1 (en) | 1996-07-23 | 1998-01-29 | Henkel Kgaa | Process for the hydrophilic finishing of fibers or nonwovens |
EP0849354A1 (en) | 1996-12-20 | 1998-06-24 | Unilever Plc | Softening compositions |
AU2006299A (en) * | 1997-12-29 | 1999-07-19 | Colgate-Palmolive Company, The | Enzyme-containing compositions having improved cleaning power |
GB0106466D0 (en) | 2001-03-15 | 2001-05-02 | Unilever Plc | Fabric softening compositions |
DE10131721C1 (en) * | 2001-06-30 | 2003-03-13 | Henkel Kgaa | Quickly soluble cleaning gel |
CN107460728B (en) * | 2017-08-30 | 2020-01-10 | 江苏金太阳纺织科技股份有限公司 | High-efficiency low-foam refining agent and preparation method thereof |
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DE3275202D1 (en) * | 1981-09-28 | 1987-02-26 | Procter & Gamble | Detergent compositions containing mixture of alkylpolysaccharide and amine oxide surfactants and fatty acid soap |
GR76287B (en) * | 1981-09-28 | 1984-08-04 | Procter & Gamble | |
GR76286B (en) * | 1981-09-28 | 1984-08-04 | Procter & Gamble | |
EP0105556A1 (en) * | 1982-09-30 | 1984-04-18 | THE PROCTER & GAMBLE COMPANY | Liquid detergent composition containing nonionic and ionic surfactants |
US4488981A (en) * | 1983-09-06 | 1984-12-18 | A. E. Staley Manufacturing Company | Lower alkyl glycosides to reduce viscosity in aqueous liquid detergents |
EP0199765B1 (en) * | 1984-11-06 | 1990-05-23 | Henkel Kommanditgesellschaft auf Aktien | Monoglycosides as viscosity modifiers in detergents |
IL81353A (en) * | 1986-01-30 | 1990-08-31 | Colgate Palmolive Co | Liquid softergent having improved detergency containing alkyl glycoside |
-
1987
- 1987-01-22 IL IL81354A patent/IL81354A/en unknown
- 1987-01-23 ZA ZA87524A patent/ZA87524B/en unknown
- 1987-01-23 NZ NZ219050A patent/NZ219050A/en unknown
- 1987-01-27 GR GR870124A patent/GR870124B/en unknown
- 1987-01-27 IN IN52/DEL/87A patent/IN169745B/en unknown
- 1987-01-27 ZW ZW17/87A patent/ZW1787A1/en unknown
- 1987-01-27 PH PH34769A patent/PH25140A/en unknown
- 1987-01-27 DE DE19873702286 patent/DE3702286A1/en not_active Withdrawn
- 1987-01-28 GB GB8701853A patent/GB2185991B/en not_active Expired - Lifetime
- 1987-01-28 EG EG51/87A patent/EG18074A/en active
- 1987-01-28 SE SE8700323A patent/SE8700323L/en not_active Application Discontinuation
- 1987-01-28 IT IT47580/87A patent/IT1205727B/en active
- 1987-01-28 AU AU68054/87A patent/AU600694B2/en not_active Ceased
- 1987-01-29 NO NO870366A patent/NO171796C/en unknown
- 1987-01-29 ES ES8700214A patent/ES2004203A6/en not_active Expired
- 1987-01-29 FR FR878701078A patent/FR2593515B1/en not_active Expired - Fee Related
- 1987-01-29 BR BR8700391A patent/BR8700391A/en not_active IP Right Cessation
- 1987-01-30 AR AR87306639A patent/AR242258A1/en active
- 1987-01-30 BE BE8700063A patent/BE1001831A5/en not_active IP Right Cessation
- 1987-01-30 MX MX005111A patent/MX168267B/en unknown
- 1987-01-30 JP JP62020365A patent/JPS62197495A/en active Pending
- 1987-01-30 CH CH341/87A patent/CH672138A5/de not_active IP Right Cessation
- 1987-01-30 KR KR1019870000744A patent/KR950002352B1/en active IP Right Grant
- 1987-01-30 TR TR87/0070A patent/TR24546A/en unknown
- 1987-01-30 NL NL8700230A patent/NL8700230A/en not_active Application Discontinuation
- 1987-01-30 ZM ZM10/87A patent/ZM1087A1/en unknown
- 1987-01-30 DK DK051287A patent/DK51287A/en not_active Application Discontinuation
-
1993
- 1993-09-23 HK HK979/93A patent/HK97993A/en unknown
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