WO2016037884A1 - Paste composition for cleaning hard surfaces - Google Patents
Paste composition for cleaning hard surfaces Download PDFInfo
- Publication number
- WO2016037884A1 WO2016037884A1 PCT/EP2015/069858 EP2015069858W WO2016037884A1 WO 2016037884 A1 WO2016037884 A1 WO 2016037884A1 EP 2015069858 W EP2015069858 W EP 2015069858W WO 2016037884 A1 WO2016037884 A1 WO 2016037884A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- abrasive
- mineral oil
- mineral
- alkyl benzene
- Prior art date
Links
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
- 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
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
Definitions
- the invention relates to a composition for removing deposits of encrusted oily or greasy stains from a hard surface.
- Hard surface cleansing compositions are meant for cleaning surfaces such as kitchen tiles, sinks, hobs, chimney, platforms and soiled articles like utensils, cutlery and crockery.
- Such surfaces are prone to heavy soiling as they often come in contact with oily or greasy substances like cooking media. Over a period of time, such deposits tend to harden or get encrusted. Oily stains and grease are usually easy to remove when they are not hardened or encrusted, however once encrusted, e.g., by aging or baking, the stains become particularly difficult to be removed. Cleaning is easier so long as the stain has not encrusted. If not cleaned promptly, the encrusted oil or grease can bind firmly to the hard surface.
- compositions for cleansing hard surfaces usually have high pH. However, low pH formats are also known. The high pH compositions are better at stain removal owing largely due to the highly alkaline nature. However, such compositions are harsh. On the other hand, the compositions having neutral to slightly acidic pH are not as harsh but they are not as effective either. Therefore, such compositions often contain more of hard abrasive particles, typically the ones having Moh's index above 3.5.
- compositions in the form of detergent bars having about 14 % anionic surfactant which is formed by reacting linear alkyl benzene sulphonic acid (LAS acid) with stoichiometric excess of dolomite. The reaction leads to a mixture of calcium LAS and magnesium LAS leaving a significant part of free dolomite to serve as an abrasive.
- LAS acid linear alkyl benzene sulphonic acid
- the composition contains over 70% total abrasives.
- the bars are used with an implement or scrubber made of nylon. Such an implement augments the inherent abrasive action of the composition and at levels in the range of 70%, the composition inherently has high abrasive action.
- WO2015/078679 A1 discloses a paste composition suitable for cleaning dishes.
- the composition aids removal of tough stains like burnt-on soot and/or burnt-on food and grease at perceivably lesser efforts and time in comparison to at least some of the known products.
- the paste has inorganic alkaline material with pH greater than 1 1 and reserve alkalinity greater than 45 in 1 % solution; and an abrasive having Mohs' index greater than 3.5. The strong alkaline nature of the composition augments the cleaning action of the abrasive.
- WO2015/067438 A1 discloses cleaning paste where the primary surfactant is Ca/Mg LAS obtained by reaction of LAS acid with dolomite.
- the composition also contains fatty acids or esters which gives non-gritty feel and superior soil removal.
- the compositions contain abrasive material.
- WO2004013268 A1 (Unilever) is disclosed a synergistic cleaning composition having 0.1 to 40 wt% surfactant and 0.1 to 40 wt% shape selective particulate abrasive having roundness factor of 0.6 to 1 .0.
- Dolomite is used for neutralization of linear alkyl benzene sulphonic (LAS) acid leading to a mixture of linear alkyl benzene sulphonate having a mixture of calcium and magnesium as counterions.
- LAS linear alkyl benzene sulphonic
- a cream composition for cleaning hard surfaces is disclosed:
- anionic surfactant of which at least 90 parts is calcium or magnesium salt of linear alkyl benzene sulphonic acid, or a mixture of the two;
- a process for preparing a cream composition for cleaning hard surfaces comprising the steps of:
- a cream composition of the first aspect for removing deposits of encrusted oily or greasy stains from a hard surface.
- a fourth aspect is disclosed a method of removing deposits of encrusted oily or greasy stains from a hard surface, the method comprising the steps of applying thereon a composition of the first aspect and scrubbing the stained part with a scrubber or a cloth and wiping with a wet cloth.
- Disclosed cream composition for cleaning hard surfaces has:
- magnesium salt of linear alkyl benzene sulphonic acid or a mixture of the two;
- compositions disclosed herein are generally suited for cleaning hard surfaces.
- the hard surface could be any household or industrial surface, but household surfaces are specifically considered and the invention will be explained further with reference to this application.
- Typical hard surfaces include glass, wood, tiles and other ceramic materials, metal surfaces, polished stones and polished concrete; more preferably stone or concrete kitchen tops, hobs, chimneys, platforms, sink, glass windows and cooker tops and tiles.
- composition is in a cream form.
- cream as used herein, also includes the closely related "paste format" and all references to the term cream should be interpreted to include the equivalent format of paste.
- the composition essentially includes 0.5 wt% to 15 wt% anionic surfactant which is primarily responsible for cleaning action. Excess anionic surfactant often results in too much foam leading to more water being used for rinsing. At least 90% of the total anionic surfactant is calcium or magnesium salt of linear alkyl benzene sulphonic acid or a mixture of the two. This can be obtained by neutralisation of a suitable precursor of the anionic surfactant, like linear alkyl benzene sulphonic acid with an alkaline salt of calcium or magnesium, e.g., carbonate.
- a preferred method of obtaining a mixture of calcium and magnesium salts is by neutralisation of an acid precursor of the surfactant (linear alkyl benzene sulphonic acid) with a mineral from the dolomites group.
- an acid precursor of the surfactant linear alkyl benzene sulphonic acid
- a mineral from the dolomites group When stoichiometric excess of the mineral is used, a part of it is utilised for neutralisation and the unreacted part usually remains in the neutralised mass which subsequently gets incorporated into the cleansing composition to serve as a hard abrasive.
- Preferred compositions have total anionic surfactant content of 2 wt% to 12 wt%, more preferably 3 wt% to 8 wt%.
- all of the anionic surfactant content is made of calcium or magnesium salt of linear alkyl benzene sulphonic acid or a mixture of the two.
- dolomite group or generally dolomites refers to minerals with an unusual trigonal symmetry and with the general formula AB(COs)2, where A is calcium and B is magnesium.
- Dolomites can be selected from the naturally occurring materials such as Ankerite Ca(Fe, Mg, Mn) (C0 3 )2, Benstonite (Ba, Sr) 6 (Ca, Mn) 6 Mg(C0 3 )i3, Dolomite CaMg(CC>3)2 and Huntite CaMg3(CC>3)4.
- dolomite refers to a particular mineral from the class "dolomites" and its molecular formula is as given earlier.
- the basic anionic (negatively charged) unit of this class consists of a triangle where at the centre resides a carbon atom. At every corner of the triangle is an oxygen atom. The threefold symmetry of the triangle explains the trigonal symmetry that many members of this class possess.
- the structure of the dolomites group of minerals is layered in such a way that the "A" metal ions occupy one layer which is followed by a carbonate layer which is followed by the "B" metal ion layer followed by another carbonate layer.
- balance of the anionic surfactant may be any suitable surfactant such as water soluble salt of organic sulphuric reaction products having an alkyl radical containing from 8 to 22 carbon atoms, and sulphuric acid ester.
- suitable surfactant such as water soluble salt of organic sulphuric reaction products having an alkyl radical containing from 8 to 22 carbon atoms, and sulphuric acid ester.
- the anionic surfactants include alkylpoly(ethoxylates), sodium lauryl ether sulphates and methyl ester sulphonates.
- the composition may also contain other surfactants, (other than anionic). These include nonionic, cationic, amphoteric and zwitterionic surfactants. However, their role is limited to providing secondary benefits, such as foam reduction, or to augment the cleaning action of anionic surfactants. Accordingly, it is preferred that, when present, their aggregate wt% is less than 15 wt%, more preferably less than 10 wt% and most preferably in the range of 1 .5 wt% to 5 wt%.
- compositions have 0.5 wt% to 5 wt% non-ionic surfactant.
- Suitable non-ionic surfactants can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
- the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
- Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensate containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 1 1 ,000; tertiary amine oxides of structure R3NO, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxyethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides
- Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water-solubilizing group, for instance sodium 3- dodecylamino-propionate, sodium 3-dodecylaminopropane sulphonate and sodium N- 2-hydroxydodecyl-N-methyltaurate.
- Suitable cationic detergent-surfactant compounds are quaternary ammonium salts having aliphatic radical of from 8 to 18 carbon atoms, for instance cetyltrimethyl ammonium bromide.
- Suitable zwitterionic surfactants that may be used are derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic radical of from 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water-solubilising group, for instance 3-(N-N-dimethyl-N-hexadecylammonium) propane-1 -sulphonate betaine, 3-(dodecylmethyl sulphonium) propane-1 -sulphonate betaine and 3-(cetylmethylphosphonium) ethane sulphonate betaine.
- the hard surface cleaning cream composition includes 10 wt% to 50 wt% of an abrasive.
- the abrasive which is a particulate material, may be soluble or insoluble in water.
- Water soluble abrasives when used may be present in such excess to any water present in the composition so that the solubility of the abrasive in the aqueous phase is exceeded and consequently the abrasive exists in the composition.
- Preferred compositions contain 30 wt% to 50 wt% abrasive, which may be one abrasive or a mixture of different abrasives.
- Moh's index of the abrasive is in the range of 2.5 to 6.0.
- the abrasive is clay, calcite, dolomite, feldspar, apatite, fluorite and hematite, kyanite, magnetite orthoclase or pumice.
- More preferred abrasives are clay, calcite, dolomite and feldspar, and optimally a combination of calcite and dolomite.
- the average particle size of each abrasive is 0.5 ⁇ to 400 ⁇ , more preferably 10 ⁇ to 200 ⁇ .
- the viscosity of preferred cream compositions is in the range of 600 cps to 1200 cps.
- the viscosity can be measured by any known means/procedure. It is preferred that viscosity is measured by a Controlled-stress Rheometer, Ex. TA Instruments AR 1000 series. Parallel flat plate geometry having diameter of 4 cm is used. The gap between the plate and the base is set to 1000 mm. Data is analyzed by the TA data analysis software. A sample of the paste is placed on the base and the plate is brought to the set geometry gap. The viscosity is measured at shear rates varying from 10 to 25 s "1 and reported at 20 s "1 .
- the pH of the compositions is in the range of 6 to 7.5, more preferably 6 to 7.
- the pH is measured at 25 °C of a neat (undiluted) sample.
- the paste/cream compositions further include 20 to 60 wt% water, preferably 30 to 65 wt% and more preferably 40 to 65 wt%.
- Mineral oil preferably 20 to 60 wt% water, preferably 30 to 65 wt% and more preferably 40 to 65 wt%.
- compositions include 0.5 wt% to 4 wt% mineral oil.
- the composition includes 2 wt% to 4 wt% of mineral oil.
- the mineral oil is a hydrocarbon having 14 to 40 carbon atoms.
- alkanes are tetra-decane, penta-decane, hexadecane, octa-decane, nonadecane, icosane and henicosane and examples of mixtures of alkanes are light liquid paraffin/light mineral oil (14 to 16 carbon atoms), heavy liquid paraffin/heavy mineral oil (more than 20 carbon atoms).
- Other mineral oils include white oil, liquid paraffin, pariffinum liquidum, liquid petroleum and perfumed mineral oil.
- the hydrocarbons may have linear, branched at any carbon atom or cyclic structures.
- the preferred mineral oil is light liquid paraffin oil with 14 to 16 carbon atoms.
- mineral oil acts synergistically with the abrasive and provides higher degree of encrusted oil/grease removal.
- the composition according may contain other ingredients that aid the cleaning performance.
- the composition may contain builders such as citrates, dicarboxylic acids, water-soluble phosphates especially polyphosphates, mixtures of ortho- and pyrophosphates, zeolites, sodium carbonate, sodium silicate, disodium silicate, sodium meta silicate and mixtures thereof.
- builders can additionally function as abrasives if present in an amount in excess of their solubility in water.
- various other optional ingredients such as structurants, colourants, soil suspending agents, detersive enzymes, perfume and preservatives may be included for their respectively known benefits.
- a process for preparing a cream composition for cleaning hard surfaces comprising the steps of: (i) neutralizing at least 90 parts by weight of linear alkyl benzene sulphonic acid with a mineral of dolomites group;
- a cream composition of the first aspect for removing deposits of encrusted oily or greasy stains from a hard surface.
- a method of removing deposits of encrusted oily or greasy stains from a hard surface comprising the steps of applying thereon a composition of the first aspect, scrubbing the stained part with a scrubber or a cloth and wiping with a wet cloth.
- the composition is spread uniformly over the surface.
- the paste is left on the surface for some time, scrubbed with a scrubber and then rinsed or wiped with a tissue paper/cloth till completely dry.
- the dried treated surface is observed to show superior soil removal.
- Example 1 Preparation of a control composition A premix was prepared by mixing 5 g commercial grade sodium carbonate in 92 g de- mineralised water at 50 ° C. To this premix was added 32 g of LAS acid (Linear alkyl benzene sulphonic acid, (Reliance Industries, India)) and the contents were further mixed for five minutes for neutralization. Completion of the reaction was confirmed by checking pH of the mix; and pH of 8 or more indicates complete neutralisation. To this neutralised mass, 5 g methyl laurate was added and mixed, which was followed by addition of 18 g of C12-3EO non-ionic surfactant. Mixing continued for two more minutes. This premix was stored in an oven maintained at 50 ° C.
- LAS acid Linear alkyl benzene sulphonic acid, (Reliance Industries, India)
- an antifoam silicone emulsion was mixed with 358 g demineralised water at 50 ° C.
- 35 g sodium carbonate was added and mixed, followed by addition of 450 g calcite.
- 153 g of the premix described earlier was added mixing continued for five minutes. The composition was allowed to cool for one hour. Subsequently, other ingredients like colorants and perfume were added to the composition.
- Example 2 Preparation of a cream composition according to the invention A premix was prepared by mixing 10 g dolomite with 91 g de-mineralised water at 50 ° C. To this, 32 g of LAS acid (as mentioned above) was added and mixed further for 5 minutes in order to achieve complete neutralisation. Completion of the reaction was confirmed by ensuring that pH of the mix was in the range of 6 to 7.5. To this neutralized mass, 5 g of methyl laurate ester was added and mixed further, followed by addition and mixing of 17 g non-ionic surfactant (as above). This premix (245 g) was stored in an oven maintained at 50 ° C.
- LAS acid as mentioned above
- a cotton cloth was attached to the head of the ETM.
- a predetermined weight was fixed to the top of the head and the machine was allowed to run for fixed number of rotations.
- the tile was then removed from the machine, rinsed under tap water, followed by de-mineralised water and then dried in an oven at 50 °C for about thirty minutes.
- the plate was weighed. The % soil removal was calculated using the difference in the weights.
- compositions and compositions according to the invention were prepared by making suitable changes to the procedure described earlier.
- Do-LAS indicates a mixture of calcium and magnesium salt of linear alkyl
- benzene sulphonic acid obtained by neutralisation of linear alkyl benzene sulphonic acid with stoichiometric excess of "dolomite", thereby leaving significant quantity of unreacted (free) dolomite for abrasive action.
- Na-LAS sodium salt of alkyl benzene sulphonic acid obtained by the usual neutralisation reaction.
- Table 1 has a set of control compositions and a set of compositions in accordance with the invention.
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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)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP15756909.6A EP3191573B1 (en) | 2014-09-11 | 2015-08-31 | Paste composition for cleaning hard surfaces |
PL15756909T PL3191573T3 (en) | 2014-09-11 | 2015-08-31 | Paste composition for cleaning hard surfaces |
BR112017004467A BR112017004467A2 (en) | 2014-09-11 | 2015-08-31 | cream composition for cleaning hard surfaces, method of removing deposits of encrusted oil or grease stains from a hard surface, preparation process and use thereof |
EA201790596A EA031894B1 (en) | 2014-09-11 | 2015-08-31 | Paste composition for cleaning hard surfaces |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EPEP14184420.9 | 2014-09-11 | ||
EP14184420 | 2014-09-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016037884A1 true WO2016037884A1 (en) | 2016-03-17 |
Family
ID=51494224
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2015/069858 WO2016037884A1 (en) | 2014-09-11 | 2015-08-31 | Paste composition for cleaning hard surfaces |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP3191573B1 (en) |
AR (1) | AR101790A1 (en) |
BR (1) | BR112017004467A2 (en) |
EA (1) | EA031894B1 (en) |
PL (1) | PL3191573T3 (en) |
TR (1) | TR201815131T4 (en) |
WO (1) | WO2016037884A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018091226A1 (en) * | 2016-11-18 | 2018-05-24 | Unilever N.V. | Aqueous hard surface cleaning composition |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5849105A (en) * | 1996-06-14 | 1998-12-15 | Colgate Palmolive Co. | Liquid crystal compositions |
US6159925A (en) * | 2000-04-06 | 2000-12-12 | Colgate-Palmolive Co. | Acidic liquid crystal compositions |
WO2004013268A1 (en) * | 2002-07-30 | 2004-02-12 | Unilever N.V. | Abrasive hard surface cleaning compositions |
EP1460125A1 (en) * | 2003-03-18 | 2004-09-22 | Unilever Plc | Abrasive hard surface cleaning compositions |
US8216552B2 (en) * | 2008-11-25 | 2012-07-10 | The Procter & Gamble Company | Oral care compositions containing gel networks and fused silica |
-
2015
- 2015-08-31 PL PL15756909T patent/PL3191573T3/en unknown
- 2015-08-31 EP EP15756909.6A patent/EP3191573B1/en not_active Not-in-force
- 2015-08-31 WO PCT/EP2015/069858 patent/WO2016037884A1/en active Application Filing
- 2015-08-31 EA EA201790596A patent/EA031894B1/en not_active IP Right Cessation
- 2015-08-31 BR BR112017004467A patent/BR112017004467A2/en not_active Application Discontinuation
- 2015-08-31 TR TR2018/15131T patent/TR201815131T4/en unknown
- 2015-09-09 AR ARP150102870A patent/AR101790A1/en active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5849105A (en) * | 1996-06-14 | 1998-12-15 | Colgate Palmolive Co. | Liquid crystal compositions |
US6159925A (en) * | 2000-04-06 | 2000-12-12 | Colgate-Palmolive Co. | Acidic liquid crystal compositions |
WO2004013268A1 (en) * | 2002-07-30 | 2004-02-12 | Unilever N.V. | Abrasive hard surface cleaning compositions |
EP1460125A1 (en) * | 2003-03-18 | 2004-09-22 | Unilever Plc | Abrasive hard surface cleaning compositions |
US8216552B2 (en) * | 2008-11-25 | 2012-07-10 | The Procter & Gamble Company | Oral care compositions containing gel networks and fused silica |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018091226A1 (en) * | 2016-11-18 | 2018-05-24 | Unilever N.V. | Aqueous hard surface cleaning composition |
AU2017362556B2 (en) * | 2016-11-18 | 2019-09-12 | Unilever Global Ip Limited | Aqueous hard surface cleaning composition |
Also Published As
Publication number | Publication date |
---|---|
BR112017004467A2 (en) | 2017-12-05 |
EA201790596A1 (en) | 2017-06-30 |
TR201815131T4 (en) | 2018-11-21 |
PL3191573T3 (en) | 2019-03-29 |
AR101790A1 (en) | 2017-01-11 |
EA031894B1 (en) | 2019-03-29 |
EP3191573A1 (en) | 2017-07-19 |
EP3191573B1 (en) | 2018-08-22 |
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