WO2000020547A1 - Cleaning compositions - Google Patents

Cleaning compositions Download PDF

Info

Publication number
WO2000020547A1
WO2000020547A1 PCT/US1999/022482 US9922482W WO0020547A1 WO 2000020547 A1 WO2000020547 A1 WO 2000020547A1 US 9922482 W US9922482 W US 9922482W WO 0020547 A1 WO0020547 A1 WO 0020547A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
cleaning
polymer
compositions
present
Prior art date
Application number
PCT/US1999/022482
Other languages
English (en)
French (fr)
Inventor
Sergio Cardola
Alessandra Massa
Carla Scorsini
Original Assignee
The Procter & Gamble Company
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 The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to CA002345635A priority Critical patent/CA2345635A1/en
Priority to AU62714/99A priority patent/AU6271499A/en
Priority to BR9914271-6A priority patent/BR9914271A/pt
Priority to JP2000574646A priority patent/JP2002526641A/ja
Publication of WO2000020547A1 publication Critical patent/WO2000020547A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • C11D3/3956Liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • C11D1/721End blocked ethers

Definitions

  • the present invention relates to cleaning compositions, especially to thickened liquid cleaning compositions exhibiting effective cleaning performance and viscosity.
  • Efficient cleaning performance and viscosity of the cleaning compositions are two requirements which drive consumer acceptance of cleaning products. Effective cleaning of surfaces is important, especially on greasy and oily soils and/or where the composition is thereafter diluted. However viscosity is also a key factor in the preparation of such a cleaning composition. The viscosity of the cleaning composition must be high enough to enable the cleaning compositions to remain on the surface being cleansed for a sufficiently long period of time to ensure effective cleaning. Such a requirement is of particular utility in cleaning compositions intended to be applied "as is" to non-horizontal structural surfaces such as walls, windows and sanitary fittings such as sinks, baths, showers, wash basins and WCs. More particularly, viscosities of 10 cps to 4000 cps are suitable. It is therefore an object of the present invention to provide cleaning compositions having effective cleaning performance and viscosity.
  • Thickened cleaning compositions are known in the art.
  • the most commonly used thickener is a polycarboxylate polymer of high molecular weight i.e. in the range of 500 000 to 4 500 000. Furthermore for best results it is preferred that the polycarboxylate polymer is cross-linked.
  • EP 834 549 and EP 812 904 both describe cleaning compositions comprising such polymeric thickeners.
  • the Applicant has found disadvantages in the use of such a polymeric thickeners in that whilst the polymer provides adequate increase in viscosity, the yield stress of the composition is also increased. The effect of the increase in yield stress is that the composition can become too thick such that it does not spread easily on the surface and is therefore difficult to use and/or rinse. In addition it has been found that occasionally air bubbles may become trapped in the composition during manufacture which are difficult to remove and not consumer acceptable.
  • a cleaning composition comprising a polymeric thickening system comprising a polycarboxylate homo or copolymer having molecular weight in the range of from 500 000 to 4 500 000 and a polycarboxylate homo or copolymer having a molecular weight of from 500 to 10 000.
  • compositions of the present invention comprise a polymeric thickening system.
  • the benefits of using the polymers described herein versus others described in the art for example cellulosic polymers such as guar gum or xanthum gum, are that they are more stable in the presence of bleach (especially hypochlorite bleach), provide better thickening efficiency and do not elevate the yield stress value to levels that might cause flow problems.
  • bleach especially hypochlorite bleach
  • the polymeric thickening system of the present invention comprises at least two polycarboxylate polymers; a high molecular weight and a low polycarboxylate homo or copolymer.
  • high molecular weight it is meant a polycarboxylate homo or copolymer having a molecular weight in the range of from 500 000 to 4 500 000, more preferably from 1 000 000 to 4 000 000.
  • Most preferred high molecular weight polymers for use herein contain from 0.5% to 4% by weight of a cross-linking agent, wherein the cross-linking agent tends to interconnect linear strands of the polymers to form the resulting cross-linked products.
  • Suitable cross-linking agents include the polyalkenyl polyethers.
  • Preferred homo- polymers include the polyacrylate polymers.
  • Preferred copolymers comprise acrylic acid monomers in combination with other monomers for maleic acid, maleic anhydride, nethacylic acid, suucinic acid, vinyl ester and/or mixtures thereof.
  • Preferred monomers of the homo or copolymeric species contain a carboxylic group.
  • the molecular weight of the carboxylate group-containing monomers typically varies from 25 to 200, preferably from 50 to 150, more preferably from 75 to 125. Further, other monomers may be present in the monomeric mixture, if desired, such as ethylene and propylene, which act as diluents.
  • Preferred high molecular weight polycarboxylate polymers for use herein are the polyacrylate polymers.
  • Especially preferred polymers are those of the polyacrylate type including those sold under the trade names Carbopol® (especially Carbopol ®ETD 2691 available form Goodrich), Acrysol® ICS-1 , Polygel®, and Sokalan®.
  • Preferred polyacrylate copolymers are those containing acrylic acid and alkyl (C5-C10) acrylate as monomers, (commercially available under the tradename Carbopol® 1623, Carbopol® 695 from BF Goodrich).
  • copolymers of acrylic acid and maleic anhydride commercially available under the tradename Polygel® DB, Polygel® DV, Polygel® DA
  • copolymers of acrylic acid and vinyl ester commercially available under the tradename Polygel® DR from 3V Sigma.
  • the second component of the polymeric thickening system is a low molecular weight polycarboxylate homo or copolymer.
  • low molecular weight it is meant a polycarboxylate polymer having a molecular weight of from 500 to 10 000, more preferably from 800 to 6000, most preferably from 1000 to 4000.
  • Preferred low molecular weight homo-polymers are not cross-linked and are most preferably polyacrylates. Most preferred copolymers comprise acrylic acid in combination with at least one other type of monomer. An especially preferred low molecular weight polymer is Polygel® W30 available from 3V sigma.
  • the ratio of high molecular weight to low molecular weight polymer is preferably from 50:1 to 1 : 10, more preferably from 30:1 to 1 :1 , most preferably from 10:1 to 5:1.
  • compositions of the present invention are shear thinning, meaning viscosity is lowered with increasing shear rates. Viscosity is measured using any currently available, suitable viscosity measuring equipment. Viscosity of the composition is preferably in the range of from 10 cps to 4000 cps, more preferably from 50 to 1000cps, most preferably from 100 to 550cps when measured using a Cammed Rheometer at 25 °C and a shear rate of from 10 to 100 s ' .
  • the polymeric thickening system is preferably present at a level of from 0.1 % to 10%, more preferably from 0.5% to 5% and most preferably from 0.7 to 2%.
  • a highly preferred, but optional component of the cleaning composition described herein is a surfactant.
  • the surfactant may be selected from anionic, non-ionic, cationic, amphoteric, zwiterionic surfactants or mixtures thereof.
  • the cleaning composition comprises an anionic surfactant system as described in more detail in the Applicants copending patent application.
  • the anionic surfactant system consists of at least one linear short-chain and one branched long chain anionic surfactant.
  • the anionic surfactants are selected from sulphates, sulphonates, alkoxylated sulphates (preferably propoxylated, more preferably ethoxylated), phosphates or mixtures thereof.
  • the short chain surfactants has from 5 to 9 carbon atoms whereas the long chain surfactant has from 10 to 16 carbon atoms.
  • a preferred short-chain surfactant is C7-9 Empimin available from Albright and Wilson.
  • a preferred long-chain surfactant is C12-13 branched sulphate based on Isalchem 123 available from Albright and Wilson.
  • the surfactant system additionally comprises a branched short-chain anionic surfactant.
  • a suitable such anionic surfactant is 2 ethyl hexyl sulphate avaialble from Albright and Wilson under the tradename Empicol 0585/A.
  • compositions according to the present invention may comprise a number of optional ingredients such as bleaching agents, fatty acids, radical scavengers, antimicrobial compounds, builders, chelants, buffers, bactericides, solvents, enzymes, hydrotropes, colorants, bleach activators, soil suspenders, dye transfer agents, brighteners, anti dusting agents, dispersants, dye transfer inhibitors, pigments, perfumes and dyes.
  • optional ingredients such as bleaching agents, fatty acids, radical scavengers, antimicrobial compounds, builders, chelants, buffers, bactericides, solvents, enzymes, hydrotropes, colorants, bleach activators, soil suspenders, dye transfer agents, brighteners, anti dusting agents, dispersants, dye transfer inhibitors, pigments, perfumes and dyes.
  • a highly preferred optional ingredient according to the present invention is a hypochlorite bleaching agent, preferably an alkali metal hypochlorite.
  • the compositions of the invention are stable in the presence of this bleaching agent.
  • alkali metal hypochlorites are preferred other hypochlorite compounds may also be used herein and can be selected from calcium and magnesium hypochlorite.
  • a preferred alkali metal hypochlorite for use herein is sodium hypochlorite.
  • Compositions according to the present invention may comprise hypochlorite bleaching agents such that the content of active chlorine in the compositions is from 0.1 % to 4%, preferably from 0.5% to 2% by weight.
  • Another optional component of the present invention is an alkali metal salt of a C8-C-
  • Said fatty acids are used as suds suppressors.
  • Suitable fatty acids for use herein can be any Cs-Ci8 fatty acid, preferably fully saturated, preferably a sodium, potassium or lithium salt, more preferably the sodium salt.
  • Suitable fatty acids may be selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and mixtures of fatty acids suitably hardened, derived from natural sources such as tallow, coconut oil, ground oil and babassu oil.
  • Other suitable suds suppressors include C10-18 alkoxylated capped alcohols.
  • the suds suppressor consists of a mixture of fatty acid, preferably coconut fatty acid (e.g. Prifac 5900 available from Unichem) and alkoxylated capped alcohol, preferably C12-14 ethoxy butoxy methyl ether (e.g. Plurafac LF231 available from BASF).
  • Compositions according to the present invention comprise from 0.1 % to 2%, preferably less than 0.6% by weight of the composition of fatty acids.
  • a further optional component of the present invention is a radical scavenger.
  • Said radical scavengers are used as stabilisers.
  • a suitable radical scavenger for use herein is the aromatic molecule containing a carboxylic group ring substitution.
  • Suitable examples of radical scavengers for use herein include the meta and para-chlorobenzoic acid, benzoic acid, meta- ortho- and para- methoxybenzoic acid, meta nitrobenzoic acid, para bromobenzoic acid, salicylic acid, 5-sulphosalicylic acid, 3,5-dimethyl salicylic acid and paratoluic acid. Of the above materials, ortho-methoxybenzoic acid is preferred.
  • Compositions according to the present invention comprise from 0.01 % to 1.5% by weight, preferably from 0.1% to 0.8% by weight and more preferably from 0.2% to 0.5% by weight of the composition of radical scavengers.
  • compositions according to the present invention are preferably greater than 10, preferably greater than 11 , more preferably greater than 12. This is achieved by the addition of from 0.4% to 2% of a caustic alkali. Suitable caustic alkalis for use herein include sodium and potassium hydroxide.
  • compositions according to the present invention comprising hypochlorite preferably have a pH greater than 12 for hypochlorite stability.
  • compositions according to the present invention are preferably aqueous and preferably comprise from 80% to 95%, more preferably from 85% to 90% of water.
  • compositions according to the present invention are prepared by methods well known in the art such as the methods described in GB 1 329 086 with the exception of the polymer being pre-dispersed in an acidic water solution of pH 3 and then neutralised up to pH 7 before starting adding the other components.
  • the compositions according to the present invention can then be prepared by mixing all of the ingredients in a non-metallic apparatus at room temperature or in warm water. If fatty acid is used, it is melted before being added to the mixture.
  • the surfactant blend is first prepared by adding the short chain surfactant to the long chain surfactants. Other optionals such as perfume and the alkali metal hypochlorite are then added whilst stirring. Colourants, if present, are added after all the other ingredients have been mixed.
  • compositions according to the present invention preferably have a viscosity of from 10 cps to 4000 cps, more preferably from 50 cps to 2000 cps, most preferably from 150 cps to 1000 cps measured with a Cammed Rheometer at a temperature of 25°C and a shear rate of 15-100 s ⁇ 1.
  • the viscosity of said spraying compositions is preferably of from 15 cps to 40 cps.
  • compositions of the present invention may be used for a variety of cleaning purposes such as cleaning hard surfaces whereby said compositions thickened nature results in longer adhesion to the surface than non-thickened compositions.
  • hard surface it is meant herein any surface like bathroom, sanitary fittings such as sinks, showers, wash basins and WCs, kitchen, sinks, cooker tops, table tops, refrigerators, walls, windows and the like.
  • compositions herein may be packaged in a variety of suitable detergent packaging known to those skilled in the art.
  • the liquid compositions herein may desirably be packaged in manually operated spray dispensing containers, which are usually made of synthetic organic polymeric plastic materials.
  • the present invention also encompasses liquid cleaning compositions of the invention packaged in a spray dispenser, preferably in a trigger spray dispenser.
  • said spray-type dispensers allow to uniformly apply to a relatively large area of a surface to be cleaned the liquid cleaning compositions suitable for use according to the present invention; thereby contributing to the cleaning properties of said compositions.
  • Such spray-type dispensers are particularly suitable to clean vertical surfaces.
  • the cleaning composition is as defined hereinbefore. Accordingly, the use of a polycarboxylate polymer in a liquid cleaning composition is provided, said composition being in a sprayed form, for preventing or reducing inhalation of said composition by the user as said composition is sprayed.
  • the liquid cleaning composition is as defined hereinbefore.
  • Suitable spray-type dispensers to be used according to the present invention include manually operated foam trigger-type dispensers sold for example by Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types of dispensers are disclosed, for instance, in US-4,701 ,311 to Dunnining et al. and US-4,646,973 and US-4,538,745 both to Focarracci. Particularly preferred to be used herein are spray-type dispensers such as T 8500® or T 8900® commercially available from Continental Spray International or T 8100® commercially available from Canyon, Northern Ireland. In such a dispenser the liquid composition is divided in fine liquid droplets resulting in a spray that is directed onto the surface to be treated.
  • the composition contained in the body of said dispenser is directed through the spray-type dispenser head via energy communicated to a pumping mechanism by the user as said user activates said pumping mechanism. More particularly, in said spray-type dispenser head the composition is forced against an obstacle, e.g. a grid or a cone or the like, thereby providing shocks to help atomise the liquid composition, i.e. to help the formation of liquid droplets.
  • an obstacle e.g. a grid or a cone or the like
  • the present invention further encompasses a method for cleaning a hard surface by applying on said surface an effective amount of a composition of the invention.
  • the said composition may be applied in its neat form or after having been diluted with water.
  • Preferably said composition is diluted up to 200 times its weight of water, preferably into 50 to 150 times its weight of water and more preferably 75 to 95, before it is applied to said surface.
  • the composition When the composition is diluted prior to use (to reach a total active level in the order of 1.2%), the composition will still advantageously provide effective cleaning performance.
  • High MW polymer #1 is Polygel DR from 3Vsigma
  • High MW polymer #2 is Carbopol ETD2691 from Goodrich
  • Low MW polymer is Polygel W30 from 3Vsigma

Landscapes

  • 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)
PCT/US1999/022482 1998-10-05 1999-09-28 Cleaning compositions WO2000020547A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002345635A CA2345635A1 (en) 1998-10-05 1999-09-28 Cleaning compositions
AU62714/99A AU6271499A (en) 1998-10-05 1999-09-28 Cleaning compositions
BR9914271-6A BR9914271A (pt) 1998-10-05 1999-09-28 Composições para limpeza
JP2000574646A JP2002526641A (ja) 1998-10-05 1999-09-28 クリーニング組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP98870208.0 1998-10-05
EP98870208A EP0992574A1 (en) 1998-10-05 1998-10-05 Cleaning compositions

Publications (1)

Publication Number Publication Date
WO2000020547A1 true WO2000020547A1 (en) 2000-04-13

Family

ID=8237100

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/022482 WO2000020547A1 (en) 1998-10-05 1999-09-28 Cleaning compositions

Country Status (9)

Country Link
EP (1) EP0992574A1 (xx)
JP (1) JP2002526641A (xx)
AR (1) AR013292A1 (xx)
AU (1) AU6271499A (xx)
BR (1) BR9914271A (xx)
CA (1) CA2345635A1 (xx)
PE (1) PE20001196A1 (xx)
TR (1) TR200100935T2 (xx)
WO (1) WO2000020547A1 (xx)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017079960A1 (en) * 2015-11-13 2017-05-18 The Procter & Gamble Company Cleaning compositions containing branched alkyl sulfate surfactants and linear alkyl sulfate surfactants
JP2020169324A (ja) * 2020-06-04 2020-10-15 ザ プロクター アンド ギャンブル カンパニーThe Procter & Gamble Company 分岐状アルキルサルフェート界面活性剤及び直鎖状アルキルサルフェート界面活性剤を含有する洗浄組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0517309A1 (en) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Linear viscoelastic aqueous liquid detergent composition, especially for automatic dishwashers, of improved high temperature stability
EP0517313A1 (en) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Linear viscoelastic aqueous liquid detergent composition, especially for automatic dishwashers, of improved high temperature stability
WO1996027000A1 (en) * 1995-02-28 1996-09-06 Kay Chemical Company Concentrated liquid gel warewash detergent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0517309A1 (en) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Linear viscoelastic aqueous liquid detergent composition, especially for automatic dishwashers, of improved high temperature stability
EP0517313A1 (en) * 1991-06-07 1992-12-09 Colgate-Palmolive Company Linear viscoelastic aqueous liquid detergent composition, especially for automatic dishwashers, of improved high temperature stability
WO1996027000A1 (en) * 1995-02-28 1996-09-06 Kay Chemical Company Concentrated liquid gel warewash detergent

Also Published As

Publication number Publication date
AU6271499A (en) 2000-04-26
PE20001196A1 (es) 2000-11-10
TR200100935T2 (tr) 2001-10-22
JP2002526641A (ja) 2002-08-20
AR013292A1 (es) 2000-12-13
CA2345635A1 (en) 2000-04-13
BR9914271A (pt) 2001-07-03
EP0992574A1 (en) 2000-04-12

Similar Documents

Publication Publication Date Title
AU2006221030B2 (en) Thickened bleach compositions comprising an amine oxide and anionic polymer
US8623804B2 (en) Thickened liquid hard surface cleaning composition
CN1105181C (zh) 浓缩液体凝胶器皿洗涤剂
US5472629A (en) Thickened acid microemulsion composition
MX2010012029A (es) Metodos y composiciones liquidas de limpieza.
US5981449A (en) Acidic cleaning compositions
EP3039111B2 (en) Aqueous liquid compositions
EP0758017B1 (en) Acidic cleaning compositions
EP0502030B1 (en) Cleaning composition
US20110092407A1 (en) Light duty liquid cleaning compositions and methods of manufacture and use thereof
EP0834549A1 (en) Cleaning compositions
US6066614A (en) Cleaning compositions
EP0906390B1 (en) Cleaning compositions
EP2304010A1 (en) Light duty liquid cleaning compositions and methods of manufacture and use thereof
CA2258130C (en) Cleaning compositions
WO2000020547A1 (en) Cleaning compositions
WO2000020543A1 (en) Cleaning with short-chain surfactants
US10975332B2 (en) Home care compositions
MXPA01003520A (en) Cleaning compositions
US6140300A (en) Low-foaming cleaning compositions comprising a hypochlorite bleaching component
MXPA01003516A (en) Cleaning with short-chain surfactants
CA3150340A1 (en) Hard surface cleaning composition comprising polyalkylene glycol
NZ242382A (en) Viscoelastic aqueous liquid automatic dishwasher detergent incorporating a benzoic acid (derivative) and a cross-linked polycarboxylate thickening agent

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ CZ DE DE DK DK DM EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2345635

Country of ref document: CA

Ref document number: 2345635

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 09806049

Country of ref document: US

Ref document number: 200102470

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: IN/PCT/2001/00247/DE

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2000 574646

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2001/00935

Country of ref document: TR

WWE Wipo information: entry into national phase

Ref document number: PA/a/2001/003520

Country of ref document: MX

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase