WO2002038720A1 - Composition for cleaning hard surfaces - Google Patents
Composition for cleaning hard surfaces Download PDFInfo
- Publication number
- WO2002038720A1 WO2002038720A1 PCT/EP2001/011881 EP0111881W WO0238720A1 WO 2002038720 A1 WO2002038720 A1 WO 2002038720A1 EP 0111881 W EP0111881 W EP 0111881W WO 0238720 A1 WO0238720 A1 WO 0238720A1
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- WO
- WIPO (PCT)
- Prior art keywords
- particles
- composition according
- cleaning composition
- liquid
- particle size
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000004140 cleaning Methods 0.000 title claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003599 detergent Substances 0.000 claims abstract description 8
- 239000003086 colorant Substances 0.000 claims abstract description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 5
- 239000000499 gel Substances 0.000 abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- -1 polyethylene Polymers 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003082 abrasive agent Substances 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229960003237 betaine Drugs 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 229910021532 Calcite Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229940096386 coconut alcohol Drugs 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000002888 zwitterionic surfactant Substances 0.000 description 2
- 125000006733 (C6-C15) alkyl group Chemical group 0.000 description 1
- SIDULKZCBGMXJL-UHFFFAOYSA-N 1-dimethylphosphoryldodecane Chemical compound CCCCCCCCCCCCP(C)(C)=O SIDULKZCBGMXJL-UHFFFAOYSA-N 0.000 description 1
- KRUABTDBQQLWLS-UHFFFAOYSA-N 1-methylsulfinyltetradecane Chemical compound CCCCCCCCCCCCCCS(C)=O KRUABTDBQQLWLS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940071118 cumenesulfonate Drugs 0.000 description 1
- PZPMGGMRWAFDAM-UHFFFAOYSA-N dioxetane;sulfuric acid Chemical class C1COO1.OS(O)(=O)=O PZPMGGMRWAFDAM-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940012017 ethylenediamine Drugs 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 229940045996 isethionic acid Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- IWMMSZLFZZPTJY-UHFFFAOYSA-M sodium;3-(dodecylamino)propane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCNCCCS([O-])(=O)=O IWMMSZLFZZPTJY-UHFFFAOYSA-M 0.000 description 1
- HWCHICTXVOMIIF-UHFFFAOYSA-M sodium;3-(dodecylamino)propanoate Chemical compound [Na+].CCCCCCCCCCCCNCCC([O-])=O HWCHICTXVOMIIF-UHFFFAOYSA-M 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000010457 zeolite 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
Definitions
- the present invention relates to liquid compositions for cleaning hard surfaces. Particularly, the invention relates to clear liquid cleaning gels containing macroscopic solid particles.
- Liquid abrasive cleaning compositions for hard surfaces are well known in the art . They generally have a milky white appearance. They have sufficient viscosity at low shear stress to keep the fine abrasive particles evenly dispersed in the liquid, while at the same time they behave as true liquids when being dispensed from a bottle.
- the fine abrasive particles (powder) in these compositions generally have a particle size below 200 micron, in most cases below 100 micron.
- Well know abrasives used in such compositions are silica, calcite, feldspar and similar inorganic materials as well as several organic polymer particles, all with a oh hardness of up to 6. Although many consumers extensively use such compositions, some do not appreciate the feel or appearance of these products, or fear that they might scratch their delicate surfaces.
- Some liquid abrasive products on the market consist of a gel-like opaque liquid in which a variety of coarse and fine irregularly shaped abrasive polymer particles are dispersed varying in diameter between more than 1 mm at one end and hardly visible to the naked eye at the other end. Because of this the total product appearance is unattractive. Thus, there is a need for a new liquid hard surface cleaning product containing solid particles, which is visually appealing to the consumer and at the same time cleans effectively.
- liquid crystal cleaning compositions which are transparent or slightly turbid and contain small amounts of abrasive particles.
- the particles may be zeolites with a mean particle size of 8-10 ⁇ m, amorphous silica with a particle size of up to 300 ⁇ m or polyethylene powder with a particle size of up to 500 ⁇ m
- WOOO/65019 discloses liquid abrasive cleaning compositions containing a fine particulate abrasive and in addition thereto microcapsules containing various additional components such as perfume, silicone oil and the like. In view of the specified amount and particle size of the abrasive, the compositions are clearly not transparent or translucent .
- WOOO/36078 discloses pourable transparent laundry detergent compositions, containing at least 15% surfactant.
- the compositions are thickened to be able to suspend macroscopic capsules containing ingredients that are desirably kept separate from the concentrated and highly alkaline detergent solution. Similar compositions, also for other applications, are disclosed in GB 1303810. The capsules do not have abrasive properties.
- the invention provides liquid cleaning compositions for hard surfaces which are clear aqueous liquid gels comprising one or more detergent surfactants and macroscopic abrasive particles, which are dispersed in a stable fashion through the liquid.
- the invention further provides a process for cleaning hard surfaces comprising the step of applying to the surface a clear aqueous liquid gel which comprises one or more detergent surfactants and macroscopic abrasive particles which are evenly dispersed through the liquid.
- the cleaning compositions of the invention are clear aqueous liquid gels.
- all components of the compositions with the exception of the abrasive particles, are clearly soluble in water.
- the required viscosity to give the composition its gel consistency is obtained by the addition of suitable thickening agents that are able to give a clear solution.
- suitable thickening agents include various vegetable or microbial polysaccharide gums, such as gum arabic, xanthan, alginates and the like, and synthetic polymers e.g. homopolymers of acrylic, methacrylic or maleic acid and copolymers thereof with each other and/or other monomers such as styrene, vinyl ethers etc.
- a gel is considered to be clear if it transmits at least 50% of light at any one wavelength in the visible region i.e. between 400 and 800nm, preferably 550-700nm, measured in a 1cm cuvette in the absence of dyes and abrasive particles.
- the transmittance is at least 70%, more preferably at least 90%.
- Gels which are satisfactory for the purposes of the present invention generally have a viscosity of between 100 and 1000 mPas, preferably at least 250 mPas, more preferably 300-750 mPas at 21 sec " (measured with a Haake viscometer at 20°C) .
- the low shear rate viscosity is such that the gel is able to suspend the macroscopic particles.
- the particles are macroscopic, i.e. clearly visible separately to the naked eye. This is in contrast to most abrasive powder particles which generally have average particle size well below 0.3mm and in the vast majority of cases at most 0.1mm (lOO ⁇ m) .
- the particles according to the invention have an average particle size between 0.3 and 2.5mm, preferably more than 0.5 and at most 1.5mm.
- the visual appeal of the compositions is considerably enhanced if the particles are of fairly uniform particle size i.e. they all have a particle size within the range of plus or minus 70% of the average particle size, preferably within a range of ⁇ 50%, more preferably ⁇ 30%.
- the abrasive particles are used in an amount of at least 0.1%, preferably 0.5%. In order to retain the transparent character of the total composition the maximum amount of particles is 20%, preferably 10%, more preferably 5%.
- the particles may be made of abrasive materials known in the art.
- they may consist of granules of one or more of the well known inorganic abrasives such as silica, silicates, calcite and the like.
- They may consist of polymer granules, such as polyethylene, polypropylene, polycarbonate and the like. Particularly suitable are granules of a biodegradable polymer, such as the starch- derived plastics known in the art.
- the abrasive particles may be made of softer materials such as hard waxes and fats, hard fatty acids, hard fatty acid soaps and the like. Such materials may also be mixed with fine particles of any of the known abrasives or with other materials, preferably solid materials, suitable for improving the cleaning process and thereafter formed into granules of the required size.
- the visual appeal of the particles, and therefore the total composition is further enhanced if the particles have a certain minimum sphericity, such that the ratio between the longest and the shortest diameter of a particle in any one direction is at most 3:1, preferably at most 2:1 or even 1.5:1.
- Particularly preferred are particles with a round, preferably a smooth round shape.
- Such particles may be made by prilling processes involving making a melt of the particle material, converting it into droplets, which are thereafter cooled in a gas (air) flow.
- Various processes and suitable equipment therefore are known in the art and may be applied to the organic abrasives, provided they are sufficiently low melting.
- High melting powders such as inorganic abrasive powders may be made into suitably shaped particles by various agglomeration processes known in the art, if necessary using an aglomeration binder.
- the cleaning compositions according to the invention may consist of a colourless liquid and solid particles having their natural colour (in many cases white)
- the compositions are considerably more attractive to the consumer if the liquid and the particles have clearly different colours. They may have different shades of the same colour, e.g. dark blue particles in a light blue liquid, or preferably, the liquid and the particles have contrasting colours e.g. white particles in a blue, green or yellow liquid or vice versa, or coloured particles in a differently coloured liquid.
- the pH of the cleaning compositions may vary within wide limits and will generally be between 2 and 14. Certain surfaces are acid-sensitive and for those a composition with pH of at least 3, preferably 3.5 or even 4 is advised. Improved cleaning of greasy soils is often obtained at alkaline pH i.e. above 7, preferably above 7.5. pH above 12 is generally not required.
- compositions according to the invention comprise one or more surfactants which may be chosen from a wide range of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, examples of which are given below.
- a suitable class of anionic surfactants are water-soluble salts of organic sulphuric acid esters and sulphonic acids having in the molecular structure an alkyl group containing 8-22 C atoms or an alkylaryl group containing 6-20 C atoms in the alkyl part .
- anionic surfactants are water-soluble salts of:
- PAS especially those obtained by sulphating the fatty alcohols produced by reducing the glycerides of tallow or coconut oil; - alkylbenzene-sulphonates, such as those in which the alkyl group contains from 6 to 20 carbon atoms; secondary alkanesulphonates .
- alkylglyceryl ether sulphates especially of the ethers of fatty alcohols derived from tallow and coconut oil; fatty acid monoglyceride sulphates; sulphates of ethoxylated aliphatic alcohols containing 1-8 ethyleneoxy units; alkylphenol ethyleneoxy-ether sulphates with from 1 to 8 ethyleneoxy units per molecule and in which the alkyl groups contain from 6 to 14 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralised with alkali.
- a suitable class of nonionic surfactants can be broadly described as compounds produced by the condensation of simple alkylene oxides, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl- aromatic in nature.
- the length of the hydrophilic or polyoxyalkylene chain that is attached to any particular hydrophobic group can be readily adjusted to yield a water- soluble compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB.
- Particular examples include : - the condensation products of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut alcohol ethylene oxide condensates having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols having C6-C15 alkyl groups with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylene-diamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80% of ethyleneoxy groups by weight and having a molecular weight of from 5,000 to 11,000.
- nonionic surfactants are : - alkylglycosides, which are condensation products of long chain aliphatic alcohols and saccharides; tertiary amine oxides of structure RRRN0, where one R is an alkyl group of 8 to 20 carbon atoms and the other R's are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, e.g.
- dimethyldodecylamine oxide dimethyldodecylamine oxide
- tertiary phosphine oxides of structure RRRP0 where one R is an alkyl group of 8 to 20 carbon atoms and the other R ' s are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide
- dialkyl sulphoxides of structure RRS0 where one R is an alkyl group of from 10 to 18 carbon atoms and the other is methyl or ethyl, for instance methyl-tetradecyl sulphoxide
- - fatty acid alkylolamides alkylene oxide condensates of fatty acid alkylolamides
- alkyl mercaptans tertiary phosphine oxides of structure RRRP0, where one R is an alkyl group of 8 to 20 carbon atoms and the other R ' s are each
- Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 20 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance sodium 3- dodecylamino-propionate, sodium 3-dodecylaminopropane- sulphonate and sodium N-2-hydroxy-dodecyl-N-methyltaurate.
- Suitable cationic surfactants can be found among quaternary ammonium salts having one or two alkyl or aralkyl groups of from 8 to 20 carbon atoms and two or three small aliphatic (e.g. methyl) groups, for instance cetyltrimethyl- ammonium bromide.
- Suitable zwitterionic surfactants can be found among derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance 3- (N,N-dimethyl-N-hexadecylammonium) -propane-1- sulphonate betaine, 3- (dodecylmethyl-sulphonium) -propane-1- sulphonate betaine and 3- (cetylmethyl-phosphonium) - ethanesulphonate betaine .
- surfactants are compounds commonly used as surface-active agents described in the well- known textbooks: "Surface Active Agents” Vol.l, by Schwartz & Perry, Interscience 1949, Nol .2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon” s Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside- Taschenbuch” , H. Stache, 2nd Edn. , Carl Hauser Verlag, 1981.
- Anionic and nonionic surfactants and combinations thereof are particularly preferred. In choosing the (combination of) surfactants care should be taken that they give a clear solution. Hydrotropes such as ⁇ a xylene- or cumene- sulfonate or others known in the art may be added if necessary.
- the surfactants are generally present in an amount of at least 0.1%, but below 15%, preferably 0.5-10%, more preferably at least 1.0%.
- compositions according to the invention may contain various optional components well known in the art which improve cleaning performance or consumer appeal.
- the compositions may contain builders, chelating agents, electrolytes, organic solvents, active halogen or peroxy bleaching agents, pH regulating agents, anti-foams, antimicrobials, preservatives, perfumes, insect repellents, etc.
- the process for cleaning a hard surface involves applying to the hard surface a suitable amount of the composition according to the invention, generally followed by rubbing the composition over the surface to be cleaned using a wipe or cloth.
- the composition may be applied directly to the surface or, alternatively, the composition may be applied to the (preferably damp) wipe or cloth first and thereafter this is rubbed over the surface with the side on which the composition was applied facing the surface.
- the abrasive particles are made of polymer or other relatively soft material the compositions according to the invention are very suitable for cleaning delicate surfaces which would otherwise easily be scratched.
- a clear liquid blue coloured gel was prepared, according to the formula below, which contained fatty acid granules having a diameter of 0.8 mm ⁇ 20% dispersed therein.
- a clear liquid green coloured gel was prepared, according to the formula below, which contained polyethylene granules having a diameter of 0.8 mm ⁇ 20% dispersed therein.
- the product had a viscosity of 380 mPas at 21 sec "1 and 20°C and a pH of 11.
- a mildly acidic (pH around 4.5) hydrogen peroxide containing clear hard surface cleaning gel was prepared according to the formula below.
- Fatty acid prills containing 10% by weight (calculated on the prills) sodium bicarbonate and having a diameter of 1.0 mm ⁇ 20% were dispersed therein.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2062702A AU2062702A (en) | 2000-11-03 | 2001-10-15 | Composition for cleaning hard surfaces |
BR0115088-0A BR0115088A (pt) | 2000-11-03 | 2001-10-15 | Composição em gel de limpeza de superfìcie dura, aquosa e translúcida abrasiva e lìquida de superfìcie dura, e, processo para limpar uma superfìcie dura |
PL361062A PL196482B1 (pl) | 2000-11-03 | 2001-10-15 | Kompozycja do czyszczenia twardych powierzchni |
EP01993373A EP1337616B1 (en) | 2000-11-03 | 2001-10-15 | Composition for cleaning hard surfaces |
CA002424455A CA2424455C (en) | 2000-11-03 | 2001-10-15 | Composition for cleaning hard surfaces |
HU0303574A HUP0303574A3 (en) | 2000-11-03 | 2001-10-15 | Abrasive, clear, aqueous et liquid gel-composition for cleaning hard surfaces and method for cleaning hard surfaces |
DE60107979T DE60107979T2 (de) | 2000-11-03 | 2001-10-15 | Zusammensetzung zum reinigen von harten oberflächen |
AU2002220627A AU2002220627B2 (en) | 2000-11-03 | 2001-10-15 | Composition for cleaning hard surfaces |
AT01993373T ATE285469T1 (de) | 2000-11-03 | 2001-10-15 | Zusammensetzung zum reinigen von harten oberflächen |
JP2002542038A JP4113429B2 (ja) | 2000-11-03 | 2001-10-15 | 硬質表面を洗浄するための組成物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00203831.3 | 2000-11-03 | ||
EP00203831 | 2000-11-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002038720A1 true WO2002038720A1 (en) | 2002-05-16 |
Family
ID=8172220
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/011881 WO2002038720A1 (en) | 2000-11-03 | 2001-10-15 | Composition for cleaning hard surfaces |
Country Status (15)
Country | Link |
---|---|
EP (1) | EP1337616B1 (cs) |
JP (1) | JP4113429B2 (cs) |
AR (1) | AR031192A1 (cs) |
AT (1) | ATE285469T1 (cs) |
AU (2) | AU2002220627B2 (cs) |
BR (1) | BR0115088A (cs) |
CA (1) | CA2424455C (cs) |
CZ (1) | CZ299089B6 (cs) |
DE (1) | DE60107979T2 (cs) |
ES (1) | ES2230389T3 (cs) |
HU (1) | HUP0303574A3 (cs) |
PL (1) | PL196482B1 (cs) |
RU (1) | RU2292386C2 (cs) |
WO (1) | WO2002038720A1 (cs) |
ZA (1) | ZA200302356B (cs) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2390097A (en) * | 2002-06-28 | 2003-12-31 | Reckitt Benckiser Nv | Detergent gels containing coloured particles |
WO2004013268A1 (en) * | 2002-07-30 | 2004-02-12 | Unilever N.V. | Abrasive hard surface cleaning compositions |
GB2393908A (en) * | 2002-10-12 | 2004-04-14 | Reckitt Benckiser Inc | Thickened, abrasive containing, liquid disinfectant |
WO2004035720A1 (de) | 2002-10-16 | 2004-04-29 | Henkel Kommanditgesellschaft Auf Aktien | Transparentes abrasives reinigungsmittel, insbesondere handgeschirrspülmittel |
US7375063B2 (en) | 2004-07-21 | 2008-05-20 | Colgate-Palmolive Company | Structured body wash |
US7393820B2 (en) | 2002-10-16 | 2008-07-01 | Henkel Kommanditgesellschaft Auf Aktien | Transparent abrasive cleaning product, especially manual dishwashing liquid |
US7723282B2 (en) | 2005-04-21 | 2010-05-25 | Colgate-Palmolive Company | Liquid detergent composition |
US7749949B2 (en) | 2006-12-15 | 2010-07-06 | Colgate-Palmolive Company | Liquid detergent composition comprising an acrylic polymer/ propylene glycol ether of methyl glucose mixture |
US20110150950A1 (en) * | 2009-12-22 | 2011-06-23 | Denis Alfred Gonzales | Liquid Cleaning And/Or Cleansing Composition |
WO2011087739A1 (en) * | 2009-12-22 | 2011-07-21 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
EP1965930A4 (en) * | 2005-12-30 | 2012-09-26 | Lam Res Corp | METHOD AND SYSTEM FOR USING A TWO-PHASE SUBSTRATE CLEANING COMPOUND |
WO2012177628A1 (en) * | 2011-06-20 | 2012-12-27 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
US8440603B2 (en) | 2011-06-20 | 2013-05-14 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising a polylactic acid biodegradable abrasive |
US8445422B2 (en) | 2010-09-21 | 2013-05-21 | The Procter & Gamble Company | Liquid cleaning composition |
US8546316B2 (en) | 2010-09-21 | 2013-10-01 | The Procter & Gamble Company | Liquid detergent composition with natural abrasive particles |
US8551932B2 (en) | 2008-09-30 | 2013-10-08 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
US8569223B2 (en) | 2008-09-30 | 2013-10-29 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
US8629095B2 (en) | 2010-04-21 | 2014-01-14 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising polyurethane foam abrasive particles |
US8759270B2 (en) | 2011-06-20 | 2014-06-24 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
US8852643B2 (en) | 2011-06-20 | 2014-10-07 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
US9163201B2 (en) | 2012-10-15 | 2015-10-20 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
US9353337B2 (en) | 2010-09-21 | 2016-05-31 | The Procter & Gamble Company | Liquid cleaning composition |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG154438A1 (en) * | 2005-12-30 | 2009-08-28 | Lam Res Corp | Cleaning compound and method and system for using the cleaning compound |
EP2336286A1 (en) * | 2009-12-18 | 2011-06-22 | The Procter & Gamble Company | Composition comprising microcapsules |
JP6091045B2 (ja) * | 2010-09-30 | 2017-03-08 | 小林製薬株式会社 | 研磨剤組成物 |
RU2656334C1 (ru) * | 2017-06-13 | 2018-06-05 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Тверской государственный университет" | Способ механохимического удаления накипных отложений |
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WO1997041204A1 (en) * | 1996-04-26 | 1997-11-06 | Colgate-Palmolive Company | Liquid crystal compositions |
US5741770A (en) * | 1989-09-22 | 1998-04-21 | Colgate-Palmolive Co. | Liquid crystal composition |
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ES2131703T5 (es) * | 1993-09-14 | 2009-06-24 | THE PROCTER & GAMBLE COMPANY | Composiciones detergentes para lavado de vajillas en forma liquida o gel, suaves, que contienen proteasa. |
DK0714978T3 (da) * | 1994-11-28 | 2001-04-23 | Rhodia Chimie Sa | Gel af upolært medium og dens anvendelse til fremstilling af vandbaserede borevæsker |
-
2001
- 2001-10-15 PL PL361062A patent/PL196482B1/pl unknown
- 2001-10-15 ES ES01993373T patent/ES2230389T3/es not_active Expired - Lifetime
- 2001-10-15 ZA ZA200302356A patent/ZA200302356B/en unknown
- 2001-10-15 CZ CZ20031229A patent/CZ299089B6/cs not_active IP Right Cessation
- 2001-10-15 AT AT01993373T patent/ATE285469T1/de not_active IP Right Cessation
- 2001-10-15 RU RU2003116238/04A patent/RU2292386C2/ru not_active IP Right Cessation
- 2001-10-15 AU AU2002220627A patent/AU2002220627B2/en not_active Ceased
- 2001-10-15 JP JP2002542038A patent/JP4113429B2/ja not_active Expired - Fee Related
- 2001-10-15 DE DE60107979T patent/DE60107979T2/de not_active Expired - Lifetime
- 2001-10-15 WO PCT/EP2001/011881 patent/WO2002038720A1/en active IP Right Grant
- 2001-10-15 EP EP01993373A patent/EP1337616B1/en not_active Expired - Lifetime
- 2001-10-15 HU HU0303574A patent/HUP0303574A3/hu unknown
- 2001-10-15 BR BR0115088-0A patent/BR0115088A/pt not_active Application Discontinuation
- 2001-10-15 AU AU2062702A patent/AU2062702A/xx active Pending
- 2001-10-15 CA CA002424455A patent/CA2424455C/en not_active Expired - Fee Related
- 2001-11-02 AR ARP010105134A patent/AR031192A1/es active IP Right Grant
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US5741770A (en) * | 1989-09-22 | 1998-04-21 | Colgate-Palmolive Co. | Liquid crystal composition |
WO1997041204A1 (en) * | 1996-04-26 | 1997-11-06 | Colgate-Palmolive Company | Liquid crystal compositions |
WO2000036078A1 (en) * | 1998-12-16 | 2000-06-22 | Unilever N.V. | Pourable transparent/translucent liquid detergent composition with suspended particles |
Cited By (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2390097A (en) * | 2002-06-28 | 2003-12-31 | Reckitt Benckiser Nv | Detergent gels containing coloured particles |
WO2004003125A1 (en) * | 2002-06-28 | 2004-01-08 | Reckitt Benckiser N., V. | Detergent composition |
WO2004013268A1 (en) * | 2002-07-30 | 2004-02-12 | Unilever N.V. | Abrasive hard surface cleaning compositions |
GB2393908A (en) * | 2002-10-12 | 2004-04-14 | Reckitt Benckiser Inc | Thickened, abrasive containing, liquid disinfectant |
WO2004035720A1 (de) | 2002-10-16 | 2004-04-29 | Henkel Kommanditgesellschaft Auf Aktien | Transparentes abrasives reinigungsmittel, insbesondere handgeschirrspülmittel |
US7393820B2 (en) | 2002-10-16 | 2008-07-01 | Henkel Kommanditgesellschaft Auf Aktien | Transparent abrasive cleaning product, especially manual dishwashing liquid |
US8590550B2 (en) | 2003-06-27 | 2013-11-26 | Lam Research Corporation | Apparatus for cleaning contaminants from substrate |
US7375063B2 (en) | 2004-07-21 | 2008-05-20 | Colgate-Palmolive Company | Structured body wash |
US7723282B2 (en) | 2005-04-21 | 2010-05-25 | Colgate-Palmolive Company | Liquid detergent composition |
EP1965930A4 (en) * | 2005-12-30 | 2012-09-26 | Lam Res Corp | METHOD AND SYSTEM FOR USING A TWO-PHASE SUBSTRATE CLEANING COMPOUND |
US7749949B2 (en) | 2006-12-15 | 2010-07-06 | Colgate-Palmolive Company | Liquid detergent composition comprising an acrylic polymer/ propylene glycol ether of methyl glucose mixture |
US8569223B2 (en) | 2008-09-30 | 2013-10-29 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
US8551932B2 (en) | 2008-09-30 | 2013-10-08 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
US20110150950A1 (en) * | 2009-12-22 | 2011-06-23 | Denis Alfred Gonzales | Liquid Cleaning And/Or Cleansing Composition |
EP2338962A1 (en) * | 2009-12-22 | 2011-06-29 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
WO2011087736A1 (en) * | 2009-12-22 | 2011-07-21 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
WO2011087739A1 (en) * | 2009-12-22 | 2011-07-21 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
WO2011087744A3 (en) * | 2009-12-22 | 2011-09-29 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
EP2338964A3 (en) * | 2009-12-22 | 2011-10-19 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
WO2011087733A1 (en) * | 2009-12-22 | 2011-07-21 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
US9163200B2 (en) | 2009-12-22 | 2015-10-20 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
US8440602B2 (en) | 2009-12-22 | 2013-05-14 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising a divinyl benzene cross-linked styrene polymer |
US8680036B2 (en) * | 2009-12-22 | 2014-03-25 | The Procter & Gamble Company | Liquid cleaning composition comprising color-stable polyurethane abrasive particles |
WO2011087735A1 (en) * | 2009-12-22 | 2011-07-21 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
EP2338963A1 (en) * | 2009-12-22 | 2011-06-29 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
EP2338966A1 (en) * | 2009-12-22 | 2011-06-29 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
US8629095B2 (en) | 2010-04-21 | 2014-01-14 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising polyurethane foam abrasive particles |
US8546316B2 (en) | 2010-09-21 | 2013-10-01 | The Procter & Gamble Company | Liquid detergent composition with natural abrasive particles |
US8445422B2 (en) | 2010-09-21 | 2013-05-21 | The Procter & Gamble Company | Liquid cleaning composition |
US9353337B2 (en) | 2010-09-21 | 2016-05-31 | The Procter & Gamble Company | Liquid cleaning composition |
US8470759B2 (en) | 2011-06-20 | 2013-06-25 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising a polyhydroxy-alkanoate biodegradable abrasive |
US8440603B2 (en) | 2011-06-20 | 2013-05-14 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising a polylactic acid biodegradable abrasive |
US8703685B2 (en) | 2011-06-20 | 2014-04-22 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising polylactic acid abrasives |
US8759270B2 (en) | 2011-06-20 | 2014-06-24 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
US8852643B2 (en) | 2011-06-20 | 2014-10-07 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
WO2012177628A1 (en) * | 2011-06-20 | 2012-12-27 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
US9163201B2 (en) | 2012-10-15 | 2015-10-20 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
Also Published As
Publication number | Publication date |
---|---|
EP1337616A1 (en) | 2003-08-27 |
ATE285469T1 (de) | 2005-01-15 |
DE60107979D1 (de) | 2005-01-27 |
ZA200302356B (en) | 2004-03-26 |
EP1337616B1 (en) | 2004-12-22 |
AU2062702A (en) | 2002-05-21 |
CA2424455A1 (en) | 2002-05-16 |
AU2002220627B2 (en) | 2006-06-01 |
BR0115088A (pt) | 2003-10-07 |
HUP0303574A3 (en) | 2005-11-28 |
ES2230389T3 (es) | 2005-05-01 |
CZ299089B6 (cs) | 2008-04-23 |
HUP0303574A2 (hu) | 2004-03-29 |
JP2004514026A (ja) | 2004-05-13 |
CA2424455C (en) | 2009-10-06 |
AR031192A1 (es) | 2003-09-10 |
PL196482B1 (pl) | 2008-01-31 |
RU2292386C2 (ru) | 2007-01-27 |
JP4113429B2 (ja) | 2008-07-09 |
PL361062A1 (en) | 2004-09-20 |
DE60107979T2 (de) | 2005-05-19 |
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