EP0768368A2 - Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles - Google Patents
Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles Download PDFInfo
- Publication number
- EP0768368A2 EP0768368A2 EP96203332A EP96203332A EP0768368A2 EP 0768368 A2 EP0768368 A2 EP 0768368A2 EP 96203332 A EP96203332 A EP 96203332A EP 96203332 A EP96203332 A EP 96203332A EP 0768368 A2 EP0768368 A2 EP 0768368A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- foam
- surfactant
- detergent
- weight
- 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.)
- Withdrawn
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- 239000004753 textile Substances 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004140 cleaning Methods 0.000 title claims abstract description 28
- 239000004744 fabric Substances 0.000 title claims description 63
- 239000006260 foam Substances 0.000 claims abstract description 97
- 239000003599 detergent Substances 0.000 claims abstract description 53
- 239000004094 surface-active agent Substances 0.000 claims abstract description 27
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 18
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003380 propellant Substances 0.000 claims description 14
- 239000000443 aerosol Substances 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 238000005187 foaming Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 239000011149 active material Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 18
- -1 alkyl sulphate Chemical compound 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000835 fiber Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 230000003750 conditioning effect Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004952 Polyamide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- GHPCICSQWQDZLM-UHFFFAOYSA-N 1-(4-chlorophenyl)sulfonyl-1-methyl-3-propylurea Chemical compound CCCNC(=O)N(C)S(=O)(=O)C1=CC=C(Cl)C=C1 GHPCICSQWQDZLM-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-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
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 210000000077 angora Anatomy 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UZABCLFSICXBCM-UHFFFAOYSA-N ethoxy hydrogen sulfate Chemical class CCOOS(O)(=O)=O UZABCLFSICXBCM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical class CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0094—High foaming compositions
-
- 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
- C11D1/38—Cationic compounds
- C11D1/65—Mixtures of anionic with cationic compounds
- C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
-
- 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
- C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
-
- 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
- C11D17/0043—For use with aerosol devices
-
- 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
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/048—Soap or detergent bars or cakes with an inner core consisting of insoluble material
-
- 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
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2044—Dihydric alcohols linear
-
- 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
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
-
- 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
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- 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
- C11D1/04—Carboxylic acids or salts 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
- 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
-
- 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
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/42—Application of foam or a temporary coating on the surface to be cleaned
Definitions
- a solution usually an aqueous solution of active materials.
- the solution soaks the fabrics thereby delivering the active materials to the fibre surface.
- Suitable solutions, or washing liquors are often prepared by dissolving granular detergent products in water, or alternatively by dissolving liquid detergent in water.
- washing machines in common use in Western Europe provide a dispensing drawer which is specifically intended to mix detergent active products, either granular or liquid, with water.
- the mixture or solution is then delivered into a drum which contains the washing load (i.e. the textile fabrics).
- This method of delivery has been still further improved by the use of dispensing devices which can be filled with detergent active products and then loaded directly into the drum with the washing load.
- the high local concentrations of active materials gives the so-called "heart-of-the-wash" effect.
- impregnated sheets may be used to clean or condition fabrics if the impregnating materials include cleaning or conditioning agents.
- the present invention offers a significant discontinuity in the method of delivering detergent active materials at the fibre surface. Furthermore, the present invention offers a means of delivering high concentrations of detergent active materials to all parts of the textile fabric, and not simply to local areas of the fabric, as in the case of pretreatment. This, in turn, leads to a highly efficient process of cleaning and conditioning textile fabrics resulting in a reduced requirement for detergent active ingredients giving lower costs, lower energy requirements and environmental benefits.
- US-A 4 118 189 describes a method of washing textiles with a foamed detergent solution.
- the aqueous solution contains from 10 to 50 grams per litre of cleaning composition (from about 1% to about 5% by weight of "active" cleaning components in aqueous solution).
- the foam is formed by providing a source of compressed air which is blown into the aqueous solution, the foam is then contacted with the textiles. After collapse of the foam it is recycled by further applications of compressed air at least five times.
- compositions similar to '377 patent The surfactant level (anionic + nonionic + soap) is preferably from 0.5% to 10% by weight of the composition.
- the present invention aims to provide a foamed detergent composition for effectively cleaning textiles.
- a method of cleaning textiles is also provided for delivering detergent active materials on to the textile fabrics in the form of a high active foam.
- the foam comprises at least 20% by weight of nonionic surfactant and has a very high volume for a given weight of detergent active material due to the large amount of gas which is trapped within it.
- the foam also has a very high surface area for a given weight of detergent active material which enables the surfaces of the textile fabric to be covered by the foam thereby delivering a concentrated detergent material uniformly over the fabric and directly to the fabric surface.
- the invention relates to a foam composition for cleaning textiles comprising detergent active components, including a surfactant system.
- the surfactant system consists of anionic surfactant and nonionic surfactant, the nonionic surfactant being at a level of at least 20% by weight of the foam composition.
- Most useful foams have a density of less than 100 grams per litre, preferably less than 50 grams per litre.
- Preferred surfactants for use in the foam compositions are alkyl sulphate, alkyl ether sulphate, or mixtures thereof, at a level of at least 18% by weight of the composition.
- Surfactants may advantageously be present at levels of at least 25%, preferably at least 50% by weight.
- Nonionic surfactants are used at levels of at least 20% by weight.
- the foam composition comprises less that 50%, preferably less that 30%, more preferably less than 10% by weight of water.
- Another aspect of the invention is a method of cleaning textiles by foam having a composition as described above.
- the foam is distributed over the textiles and preferably the ratio of water present to dry fabric is less than 1:1, preferably less than 2:3, and more preferably less than 1:2.
- the foam may be distributed over the surface of the textiles manually (i.e. "handwash") or alternatively by mechanical means, any foam or foam residue on the textiles subsequently being substantially removed by application of vacuum, by blowing a gas, or by rinsing.
- the mechanical means is provided by the rotating action of a washing machine (i.e. "machine wash")
- a third aspect of the invention is a packaged product comprising
- the packaged product delivers foam compositions as described above.
- a preferred method of cleaning textile fabrics according to the present invention is by handwashing using a foam comprising detergent active materials.
- the method comprises the first step of delivering the foam over the whole surface of the textile fabric and, preferably allowing time to soak so that the concentrated detergent may act at the fibre surface.
- water may be added to give a more dilute detergent solution in which the washing process may be continued.
- the textile fabrics may finally be rinsed in clean water.
- This aspect of the invention offers particular benefits for delicate textile fabrics such as those made from wool or silk.
- the foam delivers detergent active materials to the fibre surface without the need for soaking in water.
- An alternative method of cleaning textile fabrics according to the present invention is by adding a foam comprising detergent active materials to the textile fabrics in a conventional washing machine.
- the method comprises the first step of delivering the foam over the whole surface of the textile fabric and, preferably allowing time to soak so that the concentrated detergent may act at the fibre surface.
- the foam may be effectively distributed over the surface of the textile fabric by agitation, for example by the tumbling action of the machine drum.
- water may be added to give a more dilute detergent solution in which the washing process may be continued.
- the cleaning process is highly efficient due to the mechanical work input of the washing machine effectively and rapidly distributing the foam over the whole surface of the textile fabrics. As a result lower washing temperatures and shorter cycles are possible with corresponding benefits of low energy use.
- the present invention is also concerned with a packaged product for delivering a foam comprising detergent active materials to textile fabrics.
- the means comprises a sealed container having a nozzle which can be activated by the consumer.
- the container comprises a detergent active material and a compressed propellant gas.
- the propellant forces the detergent active material out of the sealed container.
- the propellant expands to form a myriad of gas bubbles in a foam.
- the packaged product comprises an aerosol container.
- 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.
- synthetic fibres such as polyester, polyamide, etc.
- natural fibres such as cotton, hemp
- animals such as wool, angora, silk
- Foam is a coarse dispersion of gas in a relatively small amount of liquid.
- the foams of the present invention are a continuous liquid phase comprising a detergent composition, and a dispersed phase comprising a gas.
- the gas "bubbles" of the dispersed phase can vary in size from 50 micrometers to several millimetres.
- the quality of the foam is determined by assessing various foam quality attributes, such as: 1) the appearance of the foam as it is determined by the uniformity of the bubble size distribution, as well as by the actual bubble sizes, wherein small and uniformly sized bubbles are generally preferred; 2) the thickness of the foam as it is determined by the apparent foam viscosity, wherein a greater apparent foam viscosity is generally preferred; 3) the density of the foam which is preferably less than 100 g/l, more preferably less than 50g/l, even more preferably less than 20 g/l, and most preferably less than 10 g/l; and 4) the drainage of the liquid from the foam upon standing, wherein lack of drainage of the liquid is generally preferred.
- various foam quality attributes such as: 1) the appearance of the foam as it is determined by the uniformity of the bubble size distribution, as well as by the actual bubble sizes, wherein small and uniformly sized bubbles are generally preferred; 2) the thickness of the foam as it is determined by the apparent foam viscosity, wherein a greater apparent foam visco
- the surfactant system of the present invention consists of anionic surfactant and nonionic surfactant.
- additional surfactants included cationic, amphoteric and zwitterionic surfactants, which when used, are preferably incorporated at levels of less than 10%, preferably less than 5%, more preferably less than 1% by weight, and most preferably excluded.
- Anionic surfactants useful in the present invention include the conventional C11-18 alkyl benzene sulphonates ("LAS") and primary, branched chain and random C10-20 alkyl sulphates (“AS”), the secondary (2,3) alkyl sulphates of the formula CH 3 (CH 2 ) x (CHOSO 3 - M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 - M + ) CH 2 CH 3 where x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilising cation, especially sodium, unsaturated sulphates such as oleyl sulphate, the C10-18 alkyl alkoxy sulphates ("AExS”; especially EO 1-7 ethoxy sulphates), C10-18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-18
- C10-C20 conventional soaps may also be used, preferred are the branched chain C10-C16 soaps.
- Suitable nonionic surfactants include the C12-18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), as well as C10-C18 N-alkyl polyhydroxy fatty acid amides such as C12-18 N-methylglucamides (as described in WO9206154).
- AE alkyl ethoxylates
- C6-C12 alkyl phenol alkoxylates especially ethoxylates and mixed ethoxy/propoxy
- C10-C18 N-alkyl polyhydroxy fatty acid amides such as C12-18 N-methylglucamides (as described in WO9206154).
- sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. Further details of suitable detergent components may be found in standard texts, such as A. Davidsohn and B.M. Mildwidsky, Synthetic Detergents , John Wiley & Sons, 6th edition, 1978 which discloses general detergency teachings.
- the foam of the present invention is much more concentrated and comprises less water than conventional suds.
- Foam comprises less than 90%, preferably less than 75%, more preferably less than 50%, even more preferably less than 30%, and most preferably less than 15% by weight of water.
- the foam of the present invention comprises at least 20% by weight, preferably at least 25% by weight, and more preferably at least 50% by weight of a surfactant system.
- Most preferred foams for use as cleaning compositions comprise at least 18% by weight of anionic surfactant.
- suds, which are formed in conventional washing process when detergents are diluted prior to washing are formed from quite dilute solutions typically 100g of product in 10 litres of water.
- the result is a wash liquor which comprises about 99% by weight of water.
- a layer of suds may form on the surface of the wash liquor, the composition of the suds being similar to that of the wash liquor itself.
- the surfactant content of the suds will normally be much less than 1%, typically less than 0.3%. Consequently the difference between the foam of the present invention and the suds of a conventional washing process will be understood.
- suds are often considered undesirable in the washing process and antisuds agents are often employed to reduce or control them.
- the solution of detergent active agents is the medium of transport of the actives to the fibre surface
- the presence of suds can diminish washing performance. This is because the detergent actives which are in the suds are no longer dissolved in the washing liquor itself, and are not therefore efficiently transported to the fibre surface.
- the foam of the present invention is the essential medium of the washing process.
- it is intended that it is the foam itself that delivers the detergent active agents uniformly over the fibres, and not, as in conventional washing processes, an aqueous solution of the actives.
- this does not exclude the step of presoaking the textile fabrics prior to the treatment with the foam from the present invention. It is preferred that no additional water is added to the textile fibres and foam, at least during the step of the method in which the foam is uniformly distributed over the textile fabrics.
- the method of the present invention may be used to wash textile fabrics by hand (referred to herein as "handwash")
- handwash The foam is dispensed onto or around the textile fabrics to be washed, and then the foam is thoroughly distributed over the textile fabrics, if necessary, by agitating the textile fabrics and foam by hand. It is believed that the high surface area of the foam enables the active ingredients to be well-distributed over the surface of the textile fabrics. Furthermore it is believed that the intimate proximity of the active, non-diluted foam to the textile fabrics promotes excellent cleaning.
- the textile fabrics may be left to soak in the foam for anything up to several days, or even weeks. However it is preferred that the soaking time is between 1 minute and 24 hours, preferably between 5 minutes and 4 hours.
- any foam residue may subsequently be removed from the textile fabrics.
- the residue may be rinsed out using clean water or it may be removed from the textile fabrics by applying a vacuum.
- the method of the present invention is particularly well-suited to hand washing of delicate textile fabrics.
- textile fabrics comprising high levels of wool or silk may be advantageously treated in this way.
- One particular benefit is a marked reduction in local fabric damage which may occur when conventional laundry processes are used.
- the detergent composition In conventional laundry processes the detergent composition, the soiled textile fabrics and water are all brought together in a suitable container.
- At the beginning of the process there are very high local concentrations of active ingredients as they begin to dissolve in the water, but before they have been homogeneously distributed in the water.
- Such high local concentrations in solution if they happen to be present on or close to the fabric can cause local fabric damage. This is especially true in the case of high local concentrations of bleaching agents and optical brighteners in solution.
- This type of local fabric damage is avoided according to the method of the present invention. Because all of the active ingredients are uniformly distributed throughout the large volume of the foam there are no local concentrations of active materials which might cause fabric damage.
- a typical handwash composition will comprise some or all of the following components : surfactants (anionic, nonionic, cationic, amphoteric, zwitterionic), detergent builders and chelating agents, soil release polymers, optical brightener, dye transfer inhibition polymer, perfume, enzymes, colorants.
- surfactants are preferably present at a level of from 20% to 90% by weight of the composition, preferably 25% to 80% of the composition, more preferably from 30% to 50% by weight of the composition.
- Detergent builders such as fatty acids, citric acid, succinic acid, phosphate, zeolite are preferably present at a level of from 10% to 80% by weight of the composition, preferably 10% to 50% of the composition, more preferably from 12% to 20% by weight of the composition.
- Chelating agent such as phosphonate are preferably present at a level of from 0% to 5%, more preferably from 0.1% to 3% by weight of the composition.
- the method of the present invention may be used to wash textile fabrics in a conventional washing machine (referred to herein as "machine wash”).
- machine wash a washing machine
- the foam of the present invention is simply dispensed into the drum of the washing machine either before or after the soiled textile fabrics have been loaded.
- washing machines have automatic washing cycles, and many of these cycles start by the addition of water into the machine drum.
- the concentrated foam it is necessary for the concentrated foam to be thoroughly dispersed over the textile fabrics without being dissolved in solution.
- a washing machine with a washing cycle in which the drum is rotated several times (thereby distributing the foam) before any water is added.
- this does not exclude the step of presoaking the textile fabrics prior to the treatment with the foam from the present invention.
- the wash cycle may be completed by any combination of washing, rinsing, conditioning and/or drying steps, during any one of which additional wash or rinse additives may be introduced into the machine drum.
- compositions suitable for machine wash foams are similar to those described above for handwash foams.
- the packaged product comprises a sealed container, such as an essentially cylindrical bottle, having a dispensing means such as a nozzle.
- the container contains the detergent composition and a compressed gas and may be made from any material, especially aluminium, tin-plate, plastics including PET, OPP, PE or polyamide and including mixtures, laminates or other combinations of these.
- Foam is dispensed when the nozzle is activated and the detergent is released together with the gas.
- the gas acts as a propellant and expands to form many "bubbles" within the detergent composition thereby creating the foam.
- Preferred gases include fluorocarbons, chlorofluorocarbons, H-chlorofluorocarbons, alkanes such as methane, ethane, propane, butane, pentane as well as nitrogen and nitrous oxides, ammonia and derivatives, air, dimethyl ether and mixtures of these.
- the gas may be pressurised at the time of packing.
- the product may be physically separated from a compressed gas by a membrane such as rubber under tension.
- a means for pressurising the gas subsequently by mechanical action may be provided (so-called "pump and spray” systems).
- Any nozzle or nozzle / valve assembly which provides a means for releasing the mixture of detergent ingredients from the container and provides a foam is suitable for use in the present invention.
- the Precision Valve Company (Valve Précision in France) supplies a range of nozzle assemblies for various applications including shaving foams, beauty care applications and carpet cleaners under various trade names including City®, Montego®, Power Jet®, Vulcan® and Visco®. Nozzles which disperse the foam both horizontally and vertically (when the container is held upright) are available. Metering nozzles which dispense a predetermined amount of foam are also available and useful in the present invention. Metering nozzles are disclosed in WO9108965 (Precision Valve Co) and EP-A 616 953 (3M Co).
- a vertical dispensing nozzle In order for the apparatus to be effective in the method of the present invention it should deliver the foam at a rate of at least 3g per second of foam from the sealed container, more preferably at a rate of at least 10 g per second, and most preferably at a rate of at least 20 g per second.
- the product of the Example was packed into metal containers with a propellant.
- the propellant was a fluorocarbon (134a) in the ratio of 9 parts product to 1 part propellant.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatment Of Fiber Materials (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96203332A EP0768368A3 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94200867 | 1994-03-30 | ||
EP94200867 | 1994-03-30 | ||
EP94870189A EP0677577B1 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
EP96203332A EP0768368A3 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94870189A Division EP0677577B1 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
EP94870189.1 Division | 1994-12-05 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0768368A2 true EP0768368A2 (fr) | 1997-04-16 |
EP0768368A3 EP0768368A3 (fr) | 1999-10-27 |
Family
ID=26136134
Family Applications (5)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96202407A Withdrawn EP0744461A3 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
EP96203333A Withdrawn EP0768371A3 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
EP96202406A Withdrawn EP0744460A3 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
EP96203332A Withdrawn EP0768368A3 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
EP94870189A Expired - Lifetime EP0677577B1 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
Family Applications Before (3)
Application Number | Title | Priority Date | Filing Date |
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EP96202407A Withdrawn EP0744461A3 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
EP96203333A Withdrawn EP0768371A3 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
EP96202406A Withdrawn EP0744460A3 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP94870189A Expired - Lifetime EP0677577B1 (fr) | 1994-03-30 | 1994-12-05 | Compositions de nettoyage en mousse et procédé de traitement de matériaux textiles |
Country Status (16)
Country | Link |
---|---|
EP (5) | EP0744461A3 (fr) |
JP (1) | JPH09511272A (fr) |
CN (1) | CN1105169C (fr) |
AT (1) | ATE242309T1 (fr) |
AU (1) | AU2116295A (fr) |
BR (1) | BR9507336A (fr) |
CZ (1) | CZ286696A3 (fr) |
DE (1) | DE69432785T2 (fr) |
ES (1) | ES2199952T3 (fr) |
FI (1) | FI963875A (fr) |
HU (1) | HUT75204A (fr) |
MA (1) | MA23488A1 (fr) |
NO (1) | NO964069D0 (fr) |
PE (1) | PE44695A1 (fr) |
TR (1) | TR28672A (fr) |
WO (1) | WO1995027026A1 (fr) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0753558A1 (fr) * | 1995-07-13 | 1997-01-15 | The Procter & Gamble Company | Composition moussante emballée |
EP0753559B1 (fr) * | 1995-07-13 | 2004-09-22 | The Procter & Gamble Company | Procédé de nettoyage de matériaux textiles |
ES2115338T3 (es) * | 1995-07-13 | 1998-06-16 | Procter & Gamble | Composicion de espumacion para envasado. |
EP0753560A1 (fr) * | 1995-07-13 | 1997-01-15 | The Procter & Gamble Company | Mousse |
EP0753561B1 (fr) * | 1995-07-13 | 2003-05-07 | The Procter & Gamble Company | Composition moussante emballée |
DE69531936T2 (de) * | 1995-07-13 | 2004-08-12 | The Procter & Gamble Company, Cincinnati | Verpackte schäumende Zusammensetzung |
EP0839905A1 (fr) | 1996-11-05 | 1998-05-06 | The Procter & Gamble Company | Composition détergente à base de mousse contenant des enzymes |
AU5609698A (en) * | 1996-12-20 | 1998-07-17 | Procter & Gamble Company, The | Packaged personal cleansing product |
GB9626552D0 (en) * | 1996-12-20 | 1997-02-05 | Procter & Gamble | Packaged personnal cleansing product |
GB9626551D0 (en) * | 1996-12-20 | 1997-02-05 | Procter & Gamble | Packaged personal cleansing product |
GB9626463D0 (en) * | 1996-12-20 | 1997-02-05 | Procter & Gamble | Packaged personal cleansing product |
WO1999010254A1 (fr) | 1997-08-27 | 1999-03-04 | The Procter & Gamble Company | Procede de remplissage de recipients sous pression et soupape correspondante |
US20070015675A1 (en) * | 2005-07-15 | 2007-01-18 | Painter Jeffrey D | Self-pressurized spray stain remover |
CN101046051B (zh) * | 2006-03-31 | 2012-06-27 | 海尔集团公司 | 一种用于泡沫洗涤的具有特殊特性的泡沫 |
CN101617035A (zh) * | 2007-02-20 | 2009-12-30 | 诺维信公司 | 用于洗衣的酶泡沫处理 |
CN103492545A (zh) * | 2010-08-30 | 2014-01-01 | 诺维信公司 | 两次浸泡洗涤 |
WO2012028483A1 (fr) * | 2010-08-30 | 2012-03-08 | Novozymes A/S | Lavage à trempage concentré |
CN102064740B (zh) * | 2010-12-08 | 2013-06-12 | 上海理工大学 | 碟式高倍数聚光光伏发电装置 |
WO2018231750A1 (fr) | 2017-06-13 | 2018-12-20 | The Procter & Gamble Company | Procédé de traitement d'au moins un vêtement |
US20210171880A1 (en) * | 2017-12-12 | 2021-06-10 | Conopco, Inc., D/B/A Unilever | Foamable cleaning composition |
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- 1994-12-05 EP EP96203333A patent/EP0768371A3/fr not_active Withdrawn
- 1994-12-05 AT AT94870189T patent/ATE242309T1/de not_active IP Right Cessation
- 1994-12-05 EP EP96202406A patent/EP0744460A3/fr not_active Withdrawn
- 1994-12-05 EP EP96203332A patent/EP0768368A3/fr not_active Withdrawn
- 1994-12-05 DE DE69432785T patent/DE69432785T2/de not_active Expired - Lifetime
- 1994-12-05 ES ES94870189T patent/ES2199952T3/es not_active Expired - Lifetime
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- 1995-03-10 CN CN95193214A patent/CN1105169C/zh not_active Expired - Fee Related
- 1995-03-10 AU AU21162/95A patent/AU2116295A/en not_active Abandoned
- 1995-03-10 WO PCT/US1995/002781 patent/WO1995027026A1/fr not_active Application Discontinuation
- 1995-03-10 HU HU9602659A patent/HUT75204A/hu unknown
- 1995-03-10 CZ CZ962866A patent/CZ286696A3/cs unknown
- 1995-03-28 MA MA23817A patent/MA23488A1/fr unknown
- 1995-03-29 PE PE1995265235A patent/PE44695A1/es not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
---|---|
HU9602659D0 (en) | 1996-11-28 |
FI963875A0 (fi) | 1996-09-27 |
CN1105169C (zh) | 2003-04-09 |
EP0677577B1 (fr) | 2003-06-04 |
MA23488A1 (fr) | 1995-10-01 |
EP0744461A3 (fr) | 1999-10-20 |
HUT75204A (en) | 1997-04-28 |
ES2199952T3 (es) | 2004-03-01 |
CN1148867A (zh) | 1997-04-30 |
EP0768368A3 (fr) | 1999-10-27 |
EP0744460A3 (fr) | 1999-10-27 |
TR28672A (tr) | 1997-01-31 |
CZ286696A3 (en) | 1997-02-12 |
EP0744460A2 (fr) | 1996-11-27 |
FI963875A (fi) | 1996-09-27 |
NO964069L (no) | 1996-09-27 |
EP0744461A2 (fr) | 1996-11-27 |
EP0768371A2 (fr) | 1997-04-16 |
BR9507336A (pt) | 1997-09-16 |
NO964069D0 (no) | 1996-09-27 |
EP0677577A1 (fr) | 1995-10-18 |
AU2116295A (en) | 1995-10-23 |
WO1995027026A1 (fr) | 1995-10-12 |
PE44695A1 (es) | 1996-01-18 |
DE69432785D1 (de) | 2003-07-10 |
MX9604517A (es) | 1997-09-30 |
EP0768371A3 (fr) | 1999-10-27 |
JPH09511272A (ja) | 1997-11-11 |
ATE242309T1 (de) | 2003-06-15 |
DE69432785T2 (de) | 2004-04-29 |
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