EP1423494B1 - Laundry compositions for use in a tumble dryer - Google Patents
Laundry compositions for use in a tumble dryer Download PDFInfo
- Publication number
- EP1423494B1 EP1423494B1 EP02797664A EP02797664A EP1423494B1 EP 1423494 B1 EP1423494 B1 EP 1423494B1 EP 02797664 A EP02797664 A EP 02797664A EP 02797664 A EP02797664 A EP 02797664A EP 1423494 B1 EP1423494 B1 EP 1423494B1
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- EP
- European Patent Office
- Prior art keywords
- cooh
- fabric
- agent
- alkyl
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title description 11
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 21
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical compound O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 239000004744 fabric Substances 0.000 claims description 50
- 239000003352 sequestering agent Substances 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 5
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 239000002304 perfume Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004902 Softening Agent Substances 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 238000005282 brightening Methods 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 9
- 229910001428 transition metal ion Inorganic materials 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- YIQKLZYTHXTDDT-UHFFFAOYSA-H Sirius red F3B Chemical compound C1=CC(=CC=C1N=NC2=CC(=C(C=C2)N=NC3=C(C=C4C=C(C=CC4=C3[O-])NC(=O)NC5=CC6=CC(=C(C(=C6C=C5)[O-])N=NC7=C(C=C(C=C7)N=NC8=CC=C(C=C8)S(=O)(=O)[O-])S(=O)(=O)[O-])S(=O)(=O)O)S(=O)(=O)O)S(=O)(=O)[O-])S(=O)(=O)[O-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] YIQKLZYTHXTDDT-UHFFFAOYSA-H 0.000 description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 238000004900 laundering Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 231100000673 dose–response relationship Toxicity 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000002964 rayon Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Substances OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002979 fabric softener Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002385 metal-ion deposition Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 2
- QEHXDDFROMGLSP-VDBFCSKJSA-K trisodium;(2s)-2-[2-[[(1s)-1-carboxy-2-carboxylatoethyl]amino]ethylamino]butanedioate Chemical compound [Na+].[Na+].[Na+].OC(=O)C[C@@H](C([O-])=O)NCCN[C@H](C([O-])=O)CC([O-])=O QEHXDDFROMGLSP-VDBFCSKJSA-K 0.000 description 2
- HERBOKBJKVUALN-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]acetate;hydrate Chemical compound O.[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O HERBOKBJKVUALN-UHFFFAOYSA-K 0.000 description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- -1 sheet Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000009736 wetting Methods 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
- 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
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/047—Arrangements specially adapted for dry cleaning or laundry dryer related applications
-
- 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
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
Definitions
- the present invention relates to improvements to fabric treatment compositions and a process for use of the same. It is particularly concerned with a method and compositions for use with a tumble drier.
- Sequestering agents have been used in detergents since ancient times, when materials such as citric and tartaric acid were employed to obtain clear products with good solubility.
- materials such as citric and tartaric acid were employed to obtain clear products with good solubility.
- traces of metals such as ferric iron can cause discoloration of textiles and it has long been known to use sequestering agents, such as oxalic acid, to remove them.
- the environment within which laundering processes occur is similar to that in a dyeing bath. Dyed fabric is subjected to a combination of heat and water of variable purity and it is to be expected that the presence of metal ions will cause similar problems to those that occur in dyeing. In recent years, it has been suggested that sequestrants can have benefits in the laundering process.
- the laundering process comprises a series of unit operations of which several involve the wet treatment of fabrics. These can include pre-soak and pre-treatment processes, as well as the more commonplace washing/rinsing process. Often these washing and rinsing processes are mechanised. Optional processing includes machine-drying either by centrifuge or by the application of heat, as in a so-called 'tumble drier'. Treatment components can be added at various stages, for example, with detergents being added in the wash and conditioners being added in the rinse.
- WO 2000/34427 discloses the use of the sequestrant IDS (iminodisuccinic acid) at various stages within the laundry process as part of a non-bleaching detergent composition containing IDS for colour care and stain-removal benefits.
- US 5686376 discloses the possibility of adding sequestering agents in the rinse to improve colour fidelity.
- Treatment in the drier are less common. Often, treatment in the drier is restricted to the addition of perfume (from a so-called 'drier sheet') although it is also possible to treat fabrics with conditioners/softeners during this operation.
- US 6107270 discloses dryer-added fabric softener compositions that are said to provide colour and other fabric benefits. Suggested sequestering agents include TPED (Quadrol L), EDDS and NTA. US 6025321 discloses further dryer-added fabric softener composition to provide colour and other fabric benefits, suggesting the same sequestering agents.
- the present invention provides a laundry treatment process, which comprises tumble drying clothes in the presence of a chelating agent which has one nitrogen atom and at least four carboxylic acid groups per molecule, or a salt thereof.
- the present invention also provides a laundry drier sheet comprising a substrate and a chelating agent is of the general formula HOOC-(R 1 .COOH)R 2 -NR 5 -R 3 (R 4 .COOH)-COOH wherein R 1 -R 5 are each independently, C1-C5 alkyl, hydroxy-alkyl or hydrogen.
- Preferred 1-N 4-COOH chelating agents are disuccinnic acids containing a nitrogen hetero-atom. Preferred materials are amine-bridged.
- the chelating agent is of the general formula: HOOC-(R 1 .COOH)R 2 -NR 5 -R 3 (R 4 .COOH)-COOH (1) wherein R1-R5 are each independently, C1-C5 alkyl, hydroxy-alkyl or hydrogen. In this arrangement, two of the carboxylic acid groups are disposed on either side of the bridging nitrogen atom.
- R1-R4 in the formula (1) are methylene and R5 is hydrogen.
- a particularly preferred material is therefore iminodisuccinnic acid or a salt thereof.
- the structure of which is given below as formula (2). HOOC-(CH 2 .COOH)CH-NH-CH(CH 2 .COOH)-COOH (2)
- the process can be conducted in the presence of other fabric treatment agents.
- fabric treatment agents are preferably one or more of a fabric softening agents, fabric conditioning agents, perfumes, anti-static agents, dye-transfer inhibiting polymers, dye fixing agents, other sequestrants, chlorine scavenging agents, lubricants, cross-linking polymers, soil release polymers, and optical brightening agents.
- compositions that embody the present invention can be in the form of a liquid, gel, paste, foam, powder, sheet, film, deformable solid, breakable solid or combination thereof.
- a particularly preferred form is that of the drier sheet.
- Preferred sheets are non-woven, and are more preferably embossed.
- a range of suitable materials are known including a polyester/rayon (50:50 mix) in sheet form.
- Levels of sequestrant are typically such that the weight of sequestrant is in the range 0.0005-1.0%wt of the weight of cloth being placed in the drier.
- the reflectance versus wavelength profile of 1%, Direct Red 80 dyed, unfixed, woven, cotton fabric was measured using the large aperture on a Texicon ICS Spectraflash 500 TM, (excluding the UV below 420nm). Sixteen measurements were taken (using 4 cloth thicknesses over the Spectraflash aperture).
- the Direct Red 80 dyed cotton fabric was obtained from Campbell Hayward Ltd. (Springvale Works, Shawclough Rd. Waterfoot, Rossendale, Lancs. BB4 9JZ) and was not made up into garments.
- the fabric was then washed twice in demineralised water containing transition metal and water hardness ions at the following concentrations: 1.1ppm Cu 2+ : 2.0ppm Fe 3+ : 0.12ppm Mn 2+ : 2.3ppm Zn 2+ .
- concentrations 1.1ppm Cu 2+ : 2.0ppm Fe 3+ : 0.12ppm Mn 2+ : 2.3ppm Zn 2+ .
- the levels selected are quoted in the literature as being representative of the transition metal ion levels found in the main wash for soiled loads(Patent WO9403553 ).
- Water hardness was: 4°FH Ca 2+ : 2°FH Mg 2+
- Washing was performed in a vertical axis (US) machine (WhirlpoolTM Super Capacity Plus Washer) set for a 12min wash on a small load setting. Two applications of transition metal ions were performed in order to damage the fabric by transition metal ion deposition. This has the effect of changing the hue of the fabric, to give a visible blue tinge.
- the fabric was dried in a tumble dryer (WhirlpoolTM Super Capacity Dryer) after each wash.
- the swatches were rewet using demineralised water, prior to mixing in with a wet ballast load, containing white non-mercerised, desized woven cotton.
- the ballast had previously been put through a rinse cycle with demineralised water.
- the dose response characteristic of IDS was investigated using the IDS concentrations (% on total weight of fabric in the load) given in table 1 below.
- Miele NovotronicTM T454 tumble dryer was allowed to warm up on "extra dry cotton” heat setting for 5min.
- a nonwoven, embossed, polyester/rayon (50:50 mix) sheet (95gm -2 ) was loaded with 62.5g of IDS liquid sequestrant (Iminodisuccinic acid, tetrasodium salt, 40% activity ex. Nippon Shokubai). This corresponds to 1% IDS on weight of fabric for a 2.5kg load.
- the IDS solution was spread out evenly over the sheet, using a glass rod.
- the sheet was placed inside the dryer, with the 2.5kg fabric load comprising white, desized, non-mercerised, cotton ballast + five 20x20cm 'colour damaged', Direct Red 80, overlocked, cotton test swatches. The load was dried on the extra dry cotton heat setting.
- the test swatches were removed from the tumble dryer and the reflectance versus wavelength profile was measured for each using the large aperture on a Texicon ICS Spectraflash 500 TM, (excluding the UV below 420nm). Four measurements were taken per cloth (using 4 cloth thicknesses over the Spectraflash aperture) giving a total of 20 readings per wash load. This experiment was repeated for separate wash loads using concentrations of 0.5%, 0.1%, 0.01 and 0.005% IDS on weight of fabric based on a 2.5kg load. N.B. The total volume of IDS solution added onto the sheet was kept constant at 62.5g.
- washing fabric in the presence of the metal ions causes a significant lowering of reflectance at this wavelength (compare comparative A with B). Some of this loss can be recovered by wetting and drying the fabric with demineralised water (compare comparative B with C). However, it can be seen that the presence of even low levels of IDS causes a significant improvement in the recovery of mean reflectance.
- a level of 0.01% sequestrant was chosen for the investigation into the relative performances between the sequestrants listed below:
- the IDS sequestrant shows statistically better performance at equivalent weight (0.01%) than the other sequestrants (TPED, EDDS and NTA, comparatives D-F).
- Woven fabric dyed with 1% Direct Red 80 was obtained from Campbell Hayward Ltd. (Springvale Works, Shawclough Rd. Waterfoot, Rossendale, Lancs. BB4 9JZ)
- the reflectance versus wavelength profile was measured for the new fabric using the large aperture on a Texicon ICS Spectraflash 500 TM, (excluding the UV below 420nm). Sixteen measurements were taken (using 4 cloth thicknesses over the Spectraflash aperture).
- the red woven fabric was treated with transition metal ions as follows:
- the fabric was washed twice in demineralised water containing transition metal and water hardness ions at the following concentrations: 1.1ppm Cu 2+ : 2.0ppm Fe 3+ : 0.12ppm Mn 2+ : 2.3ppm Zn 2+ .
- the levels selected are quoted in literature ( WO9403553 )as being representative of the transition metal ion levels found in the main wash when soiled loads are used.
- Water hardness was: 4°FH Ca 2+ : 2°FH Mg 2+
- Washing was performed in a vertical axis (US) machine (WhirlpoolTM Super Capacity Plus Washer) set for a 12min wash on a small load setting. Two applications of transition metal ions were performed in order to damage the fabric by transition metal ion deposition. This has the effect of changing the hue of the fabric, to give a visible blue tinge.
- the fabric was dried in a tumble dryer (WhirlpoolTM Super Capacity Dryer) in between each wash.
- a 50ml solution of 2.14e -3 moles IDS in demineralised water was prepared.
- a nonwoven, embossed, polyester/rayon (50:50 mix) sheet (95gm -2 ) was loaded with the 50g IDS sequestrant solution described above.
- the IDS solution was spread out evenly over the sheet, using a glass rod.
- a US WhirlpoolTM Super Capacity Dryer was allowed to warm up for 5 minutes on permanent press/heavy setting.
- the tumble dryer sheet that had been loaded with IDS was then placed inside the dryer, with the 2.5kg fabric load (ballast + 6 test swatches).
- the load was dried using the permanent press/heavy setting for 90 minutes.
- the reflectance versus wavelength profile was measured for the treated fabrics using the large aperture on a Texicon ICS Spectraflash 500 TM, (excluding the UV below 420nm). Four measurements were taken for each piece of fabric in each load using 4 cloth thicknesses over the Spectraflash aperture. This gave 24 measurements per load and 48 readings per treatment.
- the reflectance value of the coloured fabric at 620nm is the most sensitive to the effects of transition metal ions in this system.
- the changes in reflectance at 620nm for the fabric after treatment with the various sequestrants are shown below (in table 3) for comparison.
- Table 3 Comparison with other sequestrants at equimolar concentration (2.14x10-3 moles).
- Treatment Mean reflectance at 620nm Standard Deviation 95% confidence Limits Unwashed 46.56 0.16 0.16 Damaged 35.99 0.29 0.28 IDS 44.03 4.48 1.27 TPED 38.23 1.11 0.31 EDDS 39.41 2.99 0.85 NTA 38.45 1.71 0.48
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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)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
- The present invention relates to improvements to fabric treatment compositions and a process for use of the same. It is particularly concerned with a method and compositions for use with a tumble drier.
- Sequestering agents have been used in detergents since ancient times, when materials such as citric and tartaric acid were employed to obtain clear products with good solubility. In particular traces of metals such as ferric iron can cause discoloration of textiles and it has long been known to use sequestering agents, such as oxalic acid, to remove them.
- In 1937, IG Farbenindustrie introduced the amino-carboxylic acid sequestrants for use in the dyeing industry. It is well known that traces of metals, particularly calcium, magnesium, iron, copper and aluminium are often responsible for faulty dyeing. These impurities can be present in a dye bath because of corrosion from fittings, from the water used or as carry over from a previous process. The difficulties that occur in the dyeing process are due to the sensitivity of the dyestuffs to these trivalent and divalent cations. Dyestuffs form less soluble salts with these metals and this can lead to precipitation. Additionally, many dyestuffs contain complexing groups which complex with metal ions and may lead to changes in the solubility or colour of the dye. This latter point is particularly true with the mordant dyes. Chrome dyes, on the other hand intentionally chelate chromium and the replacement of chromium with iron in the dyestuff leads to a disastrous change of colour.
- Almost everyone is aware that repeated laundering of clothes will eventually cause most colours to fade or change in tint or hue. Consequently, many products have been marketed under the banner of 'colour care'. The first of these merely omitted bleach and other components which could damage colours. Later developments have included the incorporation of agents to prevent dye loss or dye transfer.
- In certain ways, the environment within which laundering processes occur is similar to that in a dyeing bath. Dyed fabric is subjected to a combination of heat and water of variable purity and it is to be expected that the presence of metal ions will cause similar problems to those that occur in dyeing. In recent years, it has been suggested that sequestrants can have benefits in the laundering process.
- The laundering process comprises a series of unit operations of which several involve the wet treatment of fabrics. These can include pre-soak and pre-treatment processes, as well as the more commonplace washing/rinsing process. Often these washing and rinsing processes are mechanised. Optional processing includes machine-drying either by centrifuge or by the application of heat, as in a so-called 'tumble drier'. Treatment components can be added at various stages, for example, with detergents being added in the wash and conditioners being added in the rinse.
-
WO 2000/34427 US 5686376 discloses the possibility of adding sequestering agents in the rinse to improve colour fidelity. - Instances of treatment in the drier are less common. Often, treatment in the drier is restricted to the addition of perfume (from a so-called 'drier sheet') although it is also possible to treat fabrics with conditioners/softeners during this operation.
-
US 6107270 discloses dryer-added fabric softener compositions that are said to provide colour and other fabric benefits. Suggested sequestering agents include TPED (Quadrol L), EDDS and NTA.US 6025321 discloses further dryer-added fabric softener composition to provide colour and other fabric benefits, suggesting the same sequestering agents. - Persistent staining and colour loss and/or change on fabrics are major issues for many users of domestic detergent compositions. There is therefore an ongoing need to find improved sequestering agents and or the means for delivering them.
- We have determined that a particular group of sequestering agents gives an improved colour benefit and indeed even a colour restoration benefit when used in the tumble drier. It is believed that this is in some way due to the removal of metal ions associated with the fabrics either through staining or through an earlier step in the laundry process.
- It is believed that treatment with these materials prevents further transition metal ion colour damage and that such treatment can give stain removal benefits in the next wash.
- The present invention provides a laundry treatment process, which comprises tumble drying clothes in the presence of a chelating agent which has one nitrogen atom and at least four carboxylic acid groups per molecule, or a salt thereof.
- The present invention also provides a laundry drier sheet comprising a substrate and a chelating agent is of the general formula
HOOC-(R1.COOH)R2-NR5-R3(R4.COOH)-COOH
wherein R1-R5 are each independently, C1-C5 alkyl, hydroxy-alkyl or hydrogen. - Preferred 1-N 4-COOH chelating agents are disuccinnic acids containing a nitrogen hetero-atom. Preferred materials are amine-bridged.
- Preferably, the chelating agent is of the general formula:
HOOC-(R1.COOH)R2-NR5-R3(R4.COOH)-COOH (1)
wherein R1-R5 are each independently, C1-C5 alkyl, hydroxy-alkyl or hydrogen. In this arrangement, two of the carboxylic acid groups are disposed on either side of the bridging nitrogen atom. - In a preferred embodiment, R1-R4 in the formula (1) are methylene and R5 is hydrogen. A particularly preferred material is therefore iminodisuccinnic acid or a salt thereof. The structure of which is given below as formula (2).
HOOC-(CH2.COOH)CH-NH-CH(CH2.COOH)-COOH (2)
- It is envisaged that the corresponding hydroxy acids can also be used.
- The process can be conducted in the presence of other fabric treatment agents. These are preferably one or more of a fabric softening agents, fabric conditioning agents, perfumes, anti-static agents, dye-transfer inhibiting polymers, dye fixing agents, other sequestrants, chlorine scavenging agents, lubricants, cross-linking polymers, soil release polymers, and optical brightening agents.
- In its broadest aspect, compositions that embody the present invention can be in the form of a liquid, gel, paste, foam, powder, sheet, film, deformable solid, breakable solid or combination thereof.
- A particularly preferred form is that of the drier sheet. Preferred sheets are non-woven, and are more preferably embossed. A range of suitable materials are known including a polyester/rayon (50:50 mix) in sheet form. Levels of sequestrant are typically such that the weight of sequestrant is in the range 0.0005-1.0%wt of the weight of cloth being placed in the drier.
- In order that the invention may be further understood it will be described below with reference to the following nonlimiting examples.
- The reflectance versus wavelength profile of 1%, Direct Red 80 dyed, unfixed, woven, cotton fabric was measured using the large aperture on a Texicon ICS Spectraflash 500 ™, (excluding the UV below 420nm). Sixteen measurements were taken (using 4 cloth thicknesses over the Spectraflash aperture).
- The Direct Red 80 dyed cotton fabric was obtained from Campbell Hayward Ltd. (Springvale Works, Shawclough Rd. Waterfoot, Rossendale, Lancs. BB4 9JZ) and was not made up into garments.
- The fabric was then washed twice in demineralised water containing transition metal and water hardness ions at the following concentrations: 1.1ppm Cu2+: 2.0ppm Fe3+: 0.12ppm Mn2+: 2.3ppm Zn2+. The levels selected are quoted in the literature as being representative of the transition metal ion levels found in the main wash for soiled loads(Patent
WO9403553 - Washing was performed in a vertical axis (US) machine (Whirlpool™ Super Capacity Plus Washer) set for a 12min wash on a small load setting. Two applications of transition metal ions were performed in order to damage the fabric by transition metal ion deposition. This has the effect of changing the hue of the fabric, to give a visible blue tinge. The fabric was dried in a tumble dryer (Whirlpool™ Super Capacity Dryer) after each wash.
- The change in colour of the 'colour-damaged' fabric when treated with chelating agents, provides a sensitive measure of their efficacy. For these experiments, this fabric was cut into 20cm2 swatches and overlocked. The reflectance versus wavelength profile of these swatches was measured using the large aperture on a Texicon ICS Spectraflash 500 ™, (excluding the UV below 420nm) to obtain a comparative measure of damage compared to the new fabric. Here, 4 measurements were taken per swatch, using 4 cloth thicknesses over the Spectraflash aperture. Five swatches were used per drying experiment. The swatches were rewet using demineralised water, prior to mixing in with a wet ballast load, containing white non-mercerised, desized woven cotton. The ballast had previously been put through a rinse cycle with demineralised water.
- The dose response characteristic of IDS was investigated using the IDS concentrations (% on total weight of fabric in the load) given in table 1 below.
- To obtain these results a Miele Novotronic™ T454 tumble dryer was allowed to warm up on "extra dry cotton" heat setting for 5min.
- A nonwoven, embossed, polyester/rayon (50:50 mix) sheet (95gm-2) was loaded with 62.5g of IDS liquid sequestrant (Iminodisuccinic acid, tetrasodium salt, 40% activity ex. Nippon Shokubai). This corresponds to 1% IDS on weight of fabric for a 2.5kg load. The IDS solution was spread out evenly over the sheet, using a glass rod. The sheet was placed inside the dryer, with the 2.5kg fabric load comprising white, desized, non-mercerised, cotton ballast + five 20x20cm 'colour damaged', Direct Red 80, overlocked, cotton test swatches. The load was dried on the extra dry cotton heat setting.
- Once the load was dry, the test swatches were removed from the tumble dryer and the reflectance versus wavelength profile was measured for each using the large aperture on a Texicon ICS Spectraflash 500 ™, (excluding the UV below 420nm). Four measurements were taken per cloth (using 4 cloth thicknesses over the Spectraflash aperture) giving a total of 20 readings per wash load. This experiment was repeated for separate wash loads using concentrations of 0.5%, 0.1%, 0.01 and 0.005% IDS on weight of fabric based on a 2.5kg load. N.B. The total volume of IDS solution added onto the sheet was kept constant at 62.5g.
- The experiment was performed twice for each IDS concentration, giving a total of 40 reflectance readings per concentration. The average reflectance reading at 620nm for each concentration is quoted in Table 1.
- Comparison of the reflectance profiles showed that the reflectance value at 620nm was found to be the most sensitive wavelength for measuring differences in the sequestering capability of the IDS for ions on the fabric surface. The results from the dose response experiment at 620nm are shown below in Table 1. (95% confidence limits were calculated for the experiment using the Excel™ statistical analysis tool.)
Table 1 - Dose Response for IDS Example Treatment Mean Reflectance at 620nm Standard Deviation Confidence Limits Comparative A Unwashed 46.56 - - Comparative B Damaged 35.99 - - Comparative C 0% IDS 37.92 1.70 1.49 1 0.005% IDS 39.84 2.71 1.68 2 0.01% IDS 43.68 2.72 1.69 3 0.1% IDS 49.64 4.21 2.61 4 0.5% IDS 54.98 0.88 0.54 5 1% IDS 53.89 1.86 1.15 - From these results it can be seen that washing fabric in the presence of the metal ions causes a significant lowering of reflectance at this wavelength (compare comparative A with B). Some of this loss can be recovered by wetting and drying the fabric with demineralised water (compare comparative B with C). However, it can be seen that the presence of even low levels of IDS causes a significant improvement in the recovery of mean reflectance.
- A level of 0.01% sequestrant was chosen for the investigation into the relative performances between the sequestrants listed below:
- a) TPED (N, N, N', N' tetrakis (2-hydroxy propyl) ethylenediamine: available as Quadrol ™ L, 100% activity, ex BASF).
- b) EDDS (ethylene diamine disuccinic acid tri sodium salt: available as Octaquest E30 ™ ex Octel 32.7%)
- c) NTA (Nitrilotriacetic acid sodium salt monohydrate 99% ex Aldrich).
- The method used was the same as that used for examples 1-5. Results are given in table 2 below:
Table 2: - Comparison with other sequestrants Example Treatment Mol. Wt. Mean Ref. at 620nm Std. Deviation 95% Conf. Comparative A Unwashed - 46.56 0.16 0.16 Comparative B Damaged - 35.99 0.29 0.28 Comparative C 0% IDS - 37.92 1.70 1.49 6 0.01% IDS 337.1 43.68 2.72 1.69 Comparative D 0.01% EDDS 358 40 3.02 1.87 Comparative E 0.01% TPED 292.42 40 1.70 1.05 Comparative F 0.01% NTA 257 39 3.9 2.42 - From these results it can be shown that the IDS sequestrant shows statistically better performance at equivalent weight (0.01%) than the other sequestrants (TPED, EDDS and NTA, comparatives D-F).
- Woven fabric dyed with 1% Direct Red 80 (unfixed) was obtained from Campbell Hayward Ltd. (Springvale Works, Shawclough Rd. Waterfoot, Rossendale, Lancs. BB4 9JZ)
- The reflectance versus wavelength profile was measured for the new fabric using the large aperture on a Texicon ICS Spectraflash 500 ™, (excluding the UV below 420nm). Sixteen measurements were taken (using 4 cloth thicknesses over the Spectraflash aperture).
- The red woven fabric was treated with transition metal ions as follows:
- The fabric was washed twice in demineralised water containing transition metal and water hardness ions at the following concentrations: 1.1ppm Cu2+: 2.0ppm Fe3+: 0.12ppm Mn2+: 2.3ppm Zn2+. The levels selected are quoted in literature (
WO9403553 - Washing was performed in a vertical axis (US) machine (Whirlpool™ Super Capacity Plus Washer) set for a 12min wash on a small load setting. Two applications of transition metal ions were performed in order to damage the fabric by transition metal ion deposition. This has the effect of changing the hue of the fabric, to give a visible blue tinge. The fabric was dried in a tumble dryer (Whirlpool™ Super Capacity Dryer) in between each wash.
- The change in colour of the 'colour-damaged' fabric when treated with chelating agents, provides a sensitive measure of their efficacy. For these experiments, this fabric was cut into 20cm2 swatches and overlocked. The reflectance of these swatches was measured to obtain a comparative measure of damage. The reflectance versus wavelength profile was measured for the 'colour-damaged' fabric using the large aperture on a Texicon ICS Spectraflash 500 ™, (excluding the UV below 420nm). Sixteen measurements were taken (using 4 cloth thicknesses over the Spectraflash aperture)
- Six (20x20cm) overlocked swatches of the 'colour-damaged' woven fabric dyed with 1% Direct Red 80 (unfixed) were taken, dampened with demineralised water and mixed randomly into a 2.5kg ballast load (white, desized, non-mercerised woven cotton sheeting) which had previously been put through a rinse cycle with demineralised water.
-
- TPED:
- N, N, N', N' tetrakis (2-hydroxy propyl) ethylenediamine: available as Quadrol ™ L, 100% activity, ex BASF.
- EDDS:
- Ethylene diamine disuccinic acid tri sodium salt: available as Octaquest E30 ™ ex Octel 32.7%.
- NTA:
- Nitrilotriacetic acid sodium salt monohydrate 99% ex Aldrich.
- IDS:
- Iminodisuccinic acid tetra sodium salt (ex Nippon Shokubai Co. Ltd 40.2% aqueous solution)
- Moles of all sequestrants used in experiment = 2.14e-3 moles.
- A 50ml solution of 2.14e-3 moles IDS in demineralised water was prepared. A nonwoven, embossed, polyester/rayon (50:50 mix) sheet (95gm-2) was loaded with the 50g IDS sequestrant solution described above. The IDS solution was spread out evenly over the sheet, using a glass rod.
- A US Whirlpool™ Super Capacity Dryer was allowed to warm up for 5 minutes on permanent press/heavy setting. The tumble dryer sheet that had been loaded with IDS was then placed inside the dryer, with the 2.5kg fabric load (ballast + 6 test swatches). The load was dried using the permanent press/heavy setting for 90 minutes.
- The process was repeated again with a separate, identical load.
- The entire regime was repeated with the other sequestrants, TPED, NTA and EDDS.
- The reflectance versus wavelength profile was measured for the treated fabrics using the large aperture on a Texicon ICS Spectraflash 500 ™, (excluding the UV below 420nm). Four measurements were taken for each piece of fabric in each load using 4 cloth thicknesses over the Spectraflash aperture. This gave 24 measurements per load and 48 readings per treatment.
- The reflectance value of the coloured fabric at 620nm is the most sensitive to the effects of transition metal ions in this system. The changes in reflectance at 620nm for the fabric after treatment with the various sequestrants are shown below (in table 3) for comparison.
Table 3: Comparison with other sequestrants at equimolar concentration (2.14x10-3 moles). Treatment Mean reflectance at 620nm Standard Deviation 95% confidence Limits Unwashed 46.56 0.16 0.16 Damaged 35.99 0.29 0.28 IDS 44.03 4.48 1.27 TPED 38.23 1.11 0.31 EDDS 39.41 2.99 0.85 NTA 38.45 1.71 0.48 - From these figures it can be seen that the IDS containing system is significantly better than the other materials at the concentration used.
Claims (7)
- Laundry treatment process, which comprises tumble drying clothes in the presence of a chelating agent which has one nitrogen atom and at least four carboxylic acid groups per molecule, or a salt thereof.
- Process according to claim 1, wherein the chelating agent is a disuccinnic acid or a salt thereof.
- Process according to claim 2 wherein the disuccinnic acid is amine bridged.
- Process according to any of the preceding claims wherein the chelating agent is of the general formula
HOOC-(R1.COOH)R2-NR5-R3(R4.COOH)-COOH
Wherein R1-R5 are each independently, C1-C5 alkyl, hydroxy-alkyl or hydrogen. - Process according to claim 4 wherein R1-R4 are methylene and R5 is hydrogen.
- Process according to any of claims 1-5, conducted in the presence of one or more of a fabric softening agent, fabric conditioning agent, perfume, anti-static agent, dye-transfer inhibiting polymer, dye fixing agent, other sequestrant, chlorine scavenging agent, lubricants, cross-linking polymers, optical brightening agents.
- A laundry drier sheet comprising a substrate and a chelating agent of the general formula
HOOC-(R1.COOH)R2-NR5-R3(R4.COOH)-COOH
wherein R1-R5 are each independently, C1-C5 alkyl, hydroxy-alkyl or hydrogen.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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GB0121394 | 2001-09-04 | ||
GBGB0121394.1A GB0121394D0 (en) | 2001-09-04 | 2001-09-04 | Improvements relating to fabric treatment compositions and process of fabric treatment |
PCT/EP2002/009825 WO2003020861A1 (en) | 2001-09-04 | 2002-08-30 | Laundry compositions for use in a tumble dryer |
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EP1423494A1 EP1423494A1 (en) | 2004-06-02 |
EP1423494B1 true EP1423494B1 (en) | 2008-07-16 |
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EP02797664A Expired - Lifetime EP1423494B1 (en) | 2001-09-04 | 2002-08-30 | Laundry compositions for use in a tumble dryer |
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US (1) | US20050020478A1 (en) |
EP (1) | EP1423494B1 (en) |
AT (1) | ATE401387T1 (en) |
BR (1) | BR0212309A (en) |
CA (1) | CA2459083C (en) |
DE (1) | DE60227677D1 (en) |
ES (1) | ES2307825T3 (en) |
GB (1) | GB0121394D0 (en) |
WO (1) | WO2003020861A1 (en) |
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US20050076453A1 (en) * | 2002-04-22 | 2005-04-14 | Lucas Michelle Faith | Method of enhancing a fabric article |
US20040259750A1 (en) * | 2002-04-22 | 2004-12-23 | The Procter & Gamble Company | Processes and apparatuses for applying a benefit composition to one or more fabric articles during a fabric enhancement operation |
US7059065B2 (en) * | 2002-04-22 | 2006-06-13 | The Procter & Gamble Company | Fabric article treating method and apparatus |
US7681328B2 (en) * | 2002-04-22 | 2010-03-23 | The Procter & Gamble Company | Uniform delivery of compositions |
US7503127B2 (en) * | 2002-04-22 | 2009-03-17 | The Procter And Gamble Company | Electrically charged volatile material delivery method |
US7146749B2 (en) * | 2002-04-22 | 2006-12-12 | The Procter & Gamble Company | Fabric article treating apparatus with safety device and controller |
US20050076534A1 (en) * | 2002-04-22 | 2005-04-14 | Kofi Ofosu-Asante | Fabric article treating device and system with static control |
US7047663B2 (en) * | 2002-04-22 | 2006-05-23 | The Procter & Gamble Company | Fabric article treating system and method |
US20040123489A1 (en) * | 2002-04-22 | 2004-07-01 | The Procter & Gamble Company | Thermal protection of fabric article treating device |
US8091253B2 (en) * | 2004-08-26 | 2012-01-10 | The Procter & Gamble Company | Fabric article treating device and system |
CN110072985B (en) | 2016-12-15 | 2021-04-20 | 高露洁-棕榄公司 | Fabric color protection using citric acid and iminodisuccinate in fine fabric liquid detergents |
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IL116638A0 (en) * | 1995-01-12 | 1996-05-14 | Procter & Gamble | Method and compositions for laundering fabrics |
US6025321A (en) * | 1996-03-29 | 2000-02-15 | The Procter & Gamble Company | Dryer-added fabric softener composition to provide color and other fabric benefits in package in association with instructions for use |
CA2250225A1 (en) * | 1996-03-29 | 1997-10-09 | Frederick Anthony Hartman | Use of a fabric softener composition |
US5804547A (en) * | 1997-02-28 | 1998-09-08 | The Procter & Gamble Company | Dryer-activated laundry additive compositions with color care agents |
MXPA01005821A (en) * | 1998-12-10 | 2002-03-27 | Unilever Nv | Detergent compositions. |
GB9930240D0 (en) * | 1999-12-21 | 2000-02-09 | Unilever Plc | Detergent compositions |
US20030192130A1 (en) * | 2002-04-09 | 2003-10-16 | Kaaret Thomas Walter | Fabric treatment for stain release |
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2001
- 2001-09-04 GB GBGB0121394.1A patent/GB0121394D0/en not_active Ceased
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2002
- 2002-08-30 DE DE60227677T patent/DE60227677D1/en not_active Expired - Lifetime
- 2002-08-30 AT AT02797664T patent/ATE401387T1/en not_active IP Right Cessation
- 2002-08-30 WO PCT/EP2002/009825 patent/WO2003020861A1/en active IP Right Grant
- 2002-08-30 US US10/488,634 patent/US20050020478A1/en not_active Abandoned
- 2002-08-30 CA CA2459083A patent/CA2459083C/en not_active Expired - Fee Related
- 2002-08-30 EP EP02797664A patent/EP1423494B1/en not_active Expired - Lifetime
- 2002-08-30 BR BR0212309-6A patent/BR0212309A/en not_active IP Right Cessation
- 2002-08-30 ES ES02797664T patent/ES2307825T3/en not_active Expired - Lifetime
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EP1423494A1 (en) | 2004-06-02 |
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GB0121394D0 (en) | 2001-10-24 |
CA2459083A1 (en) | 2003-03-13 |
WO2003020861A1 (en) | 2003-03-13 |
ATE401387T1 (en) | 2008-08-15 |
BR0212309A (en) | 2004-10-13 |
CA2459083C (en) | 2011-12-13 |
US20050020478A1 (en) | 2005-01-27 |
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