GB2397823A - Aqueous cleaning compositions - Google Patents

Aqueous cleaning compositions Download PDF

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Publication number
GB2397823A
GB2397823A GB0302245A GB0302245A GB2397823A GB 2397823 A GB2397823 A GB 2397823A GB 0302245 A GB0302245 A GB 0302245A GB 0302245 A GB0302245 A GB 0302245A GB 2397823 A GB2397823 A GB 2397823A
Authority
GB
United Kingdom
Prior art keywords
composition
compound
ch2ch20
hydrogen peroxide
chain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB0302245A
Other versions
GB0302245D0 (en
Inventor
Stefano Arrigoni
Francesca Rosiello
Dora Zamuner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Reckitt Benckiser NV
Original Assignee
Reckitt Benckiser NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Reckitt Benckiser NV filed Critical Reckitt Benckiser NV
Priority to GB0302245A priority Critical patent/GB2397823A/en
Publication of GB0302245D0 publication Critical patent/GB0302245D0/en
Priority to AT04706720T priority patent/ATE340234T1/en
Priority to ES04706720T priority patent/ES2268626T3/en
Priority to PL377993A priority patent/PL377993A1/en
Priority to AU2004208552A priority patent/AU2004208552B2/en
Priority to DE602004002462T priority patent/DE602004002462T2/en
Priority to PCT/GB2004/000393 priority patent/WO2004067194A2/en
Priority to EP04706720A priority patent/EP1597342B1/en
Publication of GB2397823A publication Critical patent/GB2397823A/en
Withdrawn legal-status Critical Current

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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group

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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)
  • Detergent Compositions (AREA)

Abstract

Aqueous compositions that contain hydrogen peroxide, at least one detersive surfactant and an ethoxylated aliphatic phosphono compound. The composition may comprise an ethoxylated alcohol, sodium lauryl sulphate, coconut diethanolamide, a dye, a fragrance, a chelant, and water. The composition is used as a stain remover for fabrics and is stable to light.

Description

1 2397823 Aqueous Cleaning Compositions The present invention relates to
stabilised aqueous compositions that contain hydrogen peroxide.
One drawback to the use of hydrogen peroxide compositions is that without the use of a stabiliser, or a combination of stabilizers, the aqueous peroxide compositions characteristically decompose over a relatively short time period. The actual rate at which hydrogen peroxide compositions decompose will, of course, be dependent upon such factors as pH and the presence oftrace amounts of various metal impurities, such as copper or chromium, which may act to catalytically decompose the same. Moreover, at moderately elevated temperatures, the rate of decomposition of such dilute hydrogen peroxide compositions is greatly accelerated.
An objective ofthe present invention is to provide a hydrogen peroxide containing composition that is stable to light, in particular W light. Preferably the product should also be physically stable, as well as chemically stable. Ideally the product is viscose and has a viscosity of greater than 100 cps, preferably greater than 300, 400 or 500 (as measured in a Brookfield viscometer at 20 C, spindle no.2 and 15 rpm). In addition, preferably, the product is transparent.
We present as a feature of the invention a cleaning composition comprising a) hydrogen peroxide, b) an ethoxylated aliphatic phosphono compound of formula (I) (HO)(3m)0P(R(CH2CH20)nRi)m or (HO)(3m)0P(O(CH2CH20)nRI)m or (HO)(3m)0P(OR'(CH2CH20)nH)m wherein each n is independently an integer from 1 to 10; each R is independently a 1-14C alkylene or aLkenylene chain; and R' is 1-14C alkyl or alkenyl chain, provided that the total number of carbons in R and R' does not exceed 20, preferably less than 16; s c) at least one detersive surfactant; and d) water.
We have found that the compound of formula (I) provides the composition with very 0 good aesthetic properties (a transparent gel) and helps stabilise the formula even at high temperatures (around 40 C for up to 6 months).
Hydrogen peroxide is commercially available in different grades, at 8%, 35% and 50%w/v active, and it is generally stabilised by the use of chelating agents. Preferred levels of hydrogen peroxide (as 100% active) are 0.1%wt to 12%wt, preferably from 2%wt to 1 0%wt, and ideally from 4%wt to 9%wt.
Examples of preferred detersive surfactants considered in this invention are either anionic or non-ionic surfactants and mixtures thereof Preferred total levels of surfactant are from 1 to 50% w/v, ideally from 10 to 40%wt and preferably 20 to 35%wt.
The non-ionic surfactant is preferably a surfactant having a formula RO(CH2CH20)nH wherein R is a saturated or unsaturated (preferably saturated) hydrocarbon chain ranging from C 12 to C 16 and n represents the number of repeating units and is a number of from about 1 to about 12. Examples of other non-ionic surfactants include higher aliphatic primary alcohols containing 12 to 16 carbon atoms which are condensed with about three to thirteen moles of ethylene oxide.
Other examples of non-ionic surfactants include primary alcohol ethoxylates Other examples of non-ionic surfactants suitable for use in the present invention include ethylene oxide condensate products of secondary aliphatic alcohols containing 11 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available non-ionic detergents of the s foregoing type are C11-15 secondary alkanol condensed with either 9 moles of ethylene oxide (such as Tergitol 15-S-9) or 12 moles of ethylene oxide (such as Tergitol 15-S-12) marketed by Union Carbide, a subsidiary of Dow Chemical.
Octylphenoxy polyethoxyethanol type non-ionic surfactants, for example, Triton X-100, as well as amine oxides can also be used as a non-ionic surfactant in the present invention.
A further preferred class of non-ionic surfactants are the C 1 020alkanol amides, the amide being a mono or di C2-4alkanolamine.
A preferred surfactant is an anionic surfactant. Such anionic surfactants are frequently provided in a salt form, such as alkali metal salts, ammonium salts, amine salts, amino alcohol salts or magnesium salts. Contemplated as useful are one or more sulfate or sulfonate compounds including: alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkyl benzene sulfates, alkyl benzene sulfonates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffn sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl carboxylates, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl 2s isethionates, and N-acyl taurates. Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.
Preferred surfactants are also alkyl naphthalene sulfonate anionic surfactants of the formula:
R SO3M
wherein R is a straight chain or branched alkyl chain having from about 1 to about 25 carbon atoms, saturated or unsaturated, and the longest linear portion of the alkyl chain is carbon atoms or less on the average, M is a cation which makes the compound water soluble especially an alkali metal such as sodium or magnesium, ammonium or Particularly preferred are alkyl sulfate anionic surfactants of the formula (II) (II) Nil RO- (CH2CH2O)x-S O M wherein R is a straight chain or branched alkyl chain having from about 8 to about 18 carbon atoms, saturated or unsaturated, and the longest linear portion of the alkyl chain is no more thanl 5 carbon atoms, M is a cation, preferably one which makes the compound water-soluble especially an alkali metal such as sodium or magnesium, ammonium or substituted ammonium cation, and x is from O to about 4, preferably x is 2 or 3, ideally x is 2. When x is O then most preferred are the non-ethoxylated C12-15 primary and secondary alkyl sulfates, especially sodium lauryl sulfate.
In a preferred feature of the invention we have found that transparent viscose compositions of the invention are ideally formed from the combination of compounds of formula (I), (II) and a C10-20alkanol amides, the amide is preferably a C10-20 alkanolamide of a mono or di C2-4 alkanolamine.
We present as a further feature of the invention a viscose transparent cleaning composition comprising a) a compound of formula (I); b) a compound of formula (II); c) a C10-20alkanol amide, the amide is preferably a C10-20 alkanolamide of a mono or di C2-4alkanolamine; and d) water.
The chelating agent is added at a level between 0.01 to 4 %wt, preferably between 0.1-1%wt. Examples of chelating agents are described below: - the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures therefore with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
- borate builders, as well as builders containing borate-forming materials than can produce borate under detergent storage or wash conditions can also be.
- iminodisuccinic acid metal salts - polyaspartic acid metal salts.
- examples of bicarbonate and carbonate builders are the alkaline earth and the alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof. Other examples of carbonate type builders are the metal carboxy glycine and metal glycine carbonate.
- ethylene diamino tetra acetic acid and salt forms.
- water-soluble phosphonate and phosphate builders are useful for this invention.
pyrophosphate, sodium and potassium orthophosphate sodium polymetalphosphate in which the degree of polymerization ranges from 6 to 21, and salts of physic acid. Specific examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium potassium and ammonium pyrophosphate, sodium and potassium and ammonium s pyrophosphate, sodium and potassium orthophosphate, sodium polymeta!phosphate in which the degree of polymerization ranges from 6 to 21, and salts of physic acid. The polymers are used in this invention at a level between 0.01 25%w/v, preferably between 0.1 -5%w/v are water-soluble compounds. Such polymers include the polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic lo acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
Suitably the composition is an aqueous composition, preferably comprising water in an amount of at least 50%wt, more preferably at least 60%wt of the total weight of the composition.
The composition may include one or more further optional ingredients, such as buffers, inorganic salts, fragrance, chelating agents, dispersants, enzyme stabilizers, solvents, dye transfer inhibitors and polymers. The total amount of optional ingredients present in the composition is up to 25%wt, ideally up to 20%wt, or up to 1 5%wt.
Suitable inorganic salts include metal oxides and halides, such as calcium chloride, for example.
Suitable buffers include borate buffers, for example.
Preferably the composition in the form of a stain pretreating composition which is applied onto a fabric item prior to it being washed. The composition is packaged in suitable packaging to facilitate application of the composition to the fabric. The packaging could comprise, a squeezy bottle, a roller ball applicator or a spray device. An item of packaging containing the composition may constitute a further aspect of the invention, especially where the packaging item is transparent, given the light stability of the product. Preferably the packaging item is transparent. A feature of the invention is that transparent packaging items do not need to have included a VV filter.
s A further feature of the invention is a method of treating stains on fabric which method comprises applying a composition as described herein to the stained fabric.
The invention is illustrated by the following non-limiting examples % w/v Raw Materials in finished product Hydrogen Peroxide (50%) 7.5 5.5 Chelating | 0.12 0.12 Agent | Oxo Alcohol Cl3-C15 + 13 10.5 7EO and 3EO nonionic Sodium Lauryl sulphate 3.92 4.5 (2EO or 3 EO) Ethoxylated aliphatic 4.2 3.4 phosphono Coconut diethanolamide 1.5 DYE 0.001 0.001 Fragrance 0.3 0.25 Sodium hydroxide (48%) 0.5 0.4 Deionized Water 69.459 73.829 FINISHED PRODUCT 100 100 STABILITY TEST Exposed to
SUN LIGHT
Packaging: Transparent PP bottle Wil Shout fi lter a W úher Parameters time 0 1 week 2 w. 3 w. 4 w. 6 w. 8 w.
PH 4.5 4.4 4.3 4.3 4.3 4.4 4.5 Viscosity 9 1 0 850 820 873 200 320 250 H2O2 7.50 % 7.50 % 7.50 % 7.4 % 7.40 % 7.40 % 7.40 % Colour as ref. as ref. as ref. red as red red as ref.

Claims (6)

  1. Claims 1. A cleaning composition comprising s a) hydrogen peroxide, b) an
    ethoxylated aliphatic phosphono compound of formula (I) (HO)(3m)0P(R(CH2CH20)nR')m or (HO)(3m)0P(O(CH2CH20)nR' )m or (HO)(3m)0P(ORI(CH2CH20)nH)m wherein each n is independently an integer from 1 to 10; each R is independently a 1-14C alkylene or alkenylene chain and each Rat is independently 1-14C alkyl or alkenyl chain, provided that the total number of carbons in R and R' does not exceed 20; and wherein m is an integer from 1 to 3; and c) at least one detersive surfactant; and d) water.
  2. 2. A viscose transparent cleaning composition comprising a) a compound of formula (I), as defined in claim 1; b) a compound of formula (II) 2s (II) 'if RO-(CH2CH20)x-S O M wherein R is a straight chain or branched alkyl chain having from about 8 to about 18 carbon atoms, saturated or unsaturated, and the longest linear portion of the alkyl chain is carbon atoms, M is a cation, preferably one which makes the compound watersoluble especially an alkali metal such as sodium or magnesium, ammonium or substituted ammonium cation, and x is from 0 to about 4, preferably x is 2 or 3, ideally x is 2; c) a C10-20 alkanolamide, the amide is preferably a C10-20 alkanolanide of a mono or di C2-4alkanolamine; and d) water.
    lo
  3. 3. A cleaning composition as claimed in either claim 1 or 2, wherein 0. 1% wt to 12% wt of hydrogen peroxide (as 100% active) is present.
  4. 4. A cleaning composition as claimed in either claim 1 or 2, wherein 0. 1% wt to 12% wt of hydrogen peroxide (as 100% active) is present "the detersive surfactant comprises a mixture of an anionic and a nonionic surfactant".
  5. 5. A transparent packaging item containing a composition as claimed in any claim from 1 to 4.
  6. 6. A method of treating stains on fabric which method comprises applying a composition as claimed in any claim from 1 to 4 to the stained fabric.
GB0302245A 2003-01-31 2003-01-31 Aqueous cleaning compositions Withdrawn GB2397823A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
GB0302245A GB2397823A (en) 2003-01-31 2003-01-31 Aqueous cleaning compositions
AT04706720T ATE340234T1 (en) 2003-01-31 2004-01-30 AQUEOUS DETERGENT COMPOSITIONS
ES04706720T ES2268626T3 (en) 2003-01-31 2004-01-30 WATER CLEANING COMPOSITIONS.
PL377993A PL377993A1 (en) 2003-01-31 2004-01-30 Aqueous cleaning compositions
AU2004208552A AU2004208552B2 (en) 2003-01-31 2004-01-30 Aqueous cleaning compositions
DE602004002462T DE602004002462T2 (en) 2003-01-31 2004-01-30 AQUEOUS DETERGENT COMPOSITIONS
PCT/GB2004/000393 WO2004067194A2 (en) 2003-01-31 2004-01-30 Aqueous cleaning compositions
EP04706720A EP1597342B1 (en) 2003-01-31 2004-01-30 Aqueous cleaning compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB0302245A GB2397823A (en) 2003-01-31 2003-01-31 Aqueous cleaning compositions

Publications (2)

Publication Number Publication Date
GB0302245D0 GB0302245D0 (en) 2003-03-05
GB2397823A true GB2397823A (en) 2004-08-04

Family

ID=9952193

Family Applications (1)

Application Number Title Priority Date Filing Date
GB0302245A Withdrawn GB2397823A (en) 2003-01-31 2003-01-31 Aqueous cleaning compositions

Country Status (8)

Country Link
EP (1) EP1597342B1 (en)
AT (1) ATE340234T1 (en)
AU (1) AU2004208552B2 (en)
DE (1) DE602004002462T2 (en)
ES (1) ES2268626T3 (en)
GB (1) GB2397823A (en)
PL (1) PL377993A1 (en)
WO (1) WO2004067194A2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7879744B2 (en) 2007-08-30 2011-02-01 Kimberly-Clark Worldwide, Inc. Stabilized decolorizing composition
WO2012013490A1 (en) 2010-07-27 2012-02-02 Buck-Chemie Gmbh Adhering acidic sanitary cleaner and fragrancer
US8563017B2 (en) 2008-05-15 2013-10-22 Kimberly-Clark Worldwide, Inc. Disinfectant wet wipe
US8569221B2 (en) 2007-08-30 2013-10-29 Kimberly-Clark Worldwide, Inc. Stain-discharging and removing system
WO2018237103A1 (en) * 2017-06-21 2018-12-27 The Procter & Gamble Company Fabric treatment

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7658953B2 (en) 2006-01-13 2010-02-09 Aseptix Research B.V. Enhanced activity biocidal hydrogen peroxide composition
RU2437928C2 (en) * 2006-01-13 2011-12-27 Асептикс Рисерч Б.В. Biocidal compositions of hydrogen peroxide with improved activity
US11273625B2 (en) 2018-12-21 2022-03-15 The Clorox Company Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene
CA3128040A1 (en) 2019-04-02 2020-10-08 The Clorox Company Process for manufacturing multi-layer substrates comprising sandwich layers and polyethylene

Citations (1)

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Publication number Priority date Publication date Assignee Title
WO1991009807A2 (en) * 1989-12-23 1991-07-11 Interox Chemicals Limited Stabilisation of hydrogen peroxide solutions

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7879744B2 (en) 2007-08-30 2011-02-01 Kimberly-Clark Worldwide, Inc. Stabilized decolorizing composition
US8569221B2 (en) 2007-08-30 2013-10-29 Kimberly-Clark Worldwide, Inc. Stain-discharging and removing system
US8772218B2 (en) 2007-08-30 2014-07-08 Kimberly-Clark Worldwide, Inc. Stain-discharging and removing system
US8563017B2 (en) 2008-05-15 2013-10-22 Kimberly-Clark Worldwide, Inc. Disinfectant wet wipe
WO2012013490A1 (en) 2010-07-27 2012-02-02 Buck-Chemie Gmbh Adhering acidic sanitary cleaner and fragrancer
CN103153048A (en) * 2010-07-27 2013-06-12 巴克-化学有限责任公司 Adhering acidic sanitary cleaner and fragrancer
CN103153048B (en) * 2010-07-27 2015-07-22 巴克-化学有限责任公司 Adhering acidic sanitary cleaner and fragrancer
US9102906B2 (en) 2010-07-27 2015-08-11 Buck-Chemie Gmbh Adhering acidic sanitary cleaner and fragrancer
RU2573988C2 (en) * 2010-07-27 2016-01-27 Бук-Хеми Гмбх Adhesive acidic cleaning and flavouring substance for plumbing fixtures
WO2018237103A1 (en) * 2017-06-21 2018-12-27 The Procter & Gamble Company Fabric treatment

Also Published As

Publication number Publication date
DE602004002462D1 (en) 2006-11-02
EP1597342B1 (en) 2006-09-20
EP1597342A2 (en) 2005-11-23
WO2004067194A2 (en) 2004-08-12
PL377993A1 (en) 2006-02-20
AU2004208552B2 (en) 2009-05-28
DE602004002462T2 (en) 2007-09-13
GB0302245D0 (en) 2003-03-05
ATE340234T1 (en) 2006-10-15
AU2004208552A1 (en) 2004-08-12
WO2004067194A3 (en) 2004-11-18
ES2268626T3 (en) 2007-03-16

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