WO2013078949A1 - Liquid composition for cleaning of head surfaces - Google Patents

Liquid composition for cleaning of head surfaces Download PDF

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Publication number
WO2013078949A1
WO2013078949A1 PCT/CN2012/084669 CN2012084669W WO2013078949A1 WO 2013078949 A1 WO2013078949 A1 WO 2013078949A1 CN 2012084669 W CN2012084669 W CN 2012084669W WO 2013078949 A1 WO2013078949 A1 WO 2013078949A1
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WIPO (PCT)
Prior art keywords
calcium carbonate
micrometer
composition
composition according
acicular
Prior art date
Application number
PCT/CN2012/084669
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English (en)
French (fr)
Inventor
Alexander Thomas Ashcroft
Jian Cao
Vicky Marie FAWCETT
Shouwei MA
Edward George Pelan
Simeon Dobrev Stoyanov
Weizheng Zhou
Huan-jun ZHOU
Original Assignee
Unilever N.V.
Unilever Plc
Hindustan Unilever Limited
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Application filed by Unilever N.V., Unilever Plc, Hindustan Unilever Limited filed Critical Unilever N.V.
Priority to IN943MUN2014 priority Critical patent/IN2014MN00943A/en
Priority to EP12853510.1A priority patent/EP2785822A4/en
Publication of WO2013078949A1 publication Critical patent/WO2013078949A1/en
Priority to ZA2014/03699A priority patent/ZA201403699B/en

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    • 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
    • C11D3/1233—Carbonates, e.g. calcite or dolomite
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension

Definitions

  • the present invention relates to a cleaning composition for hard surfaces for household use, and to a method for cleaning hard surfaces using the composition.
  • Cleaning liquids for household surfaces are well known. These liquids often contain ingredients that have the purpose to facilitate the easy removal of stains and soils from hard surfaces while abrasion and scratching of the surface should be as low as possible.
  • Calcium carbonate is often used as an abrasive in such cleaning liquids, and tough soil on surfaces may be removed via these liquid abrasive cleaners.
  • Calcium carbonate (CaC0 3 ) of known particle size, in the calcite crystal form, is used as the abrasive in current commercially available liquid abrasive cleaners. This abrasive is a highly effective tough soil remover, but with this presents the unavoidable potential for surface damage when cleaning. Increasing the level of calcite in the formulation improves cleaning, but also increases surface damage.
  • EP 0 103 325 A1 discloses a liquid scouring cleaning composition
  • a liquid scouring cleaning composition comprising an abrasive powder, for example precipitated calcium carbonate (aragonite).
  • aragonite precipitated calcium carbonate
  • Aragonite is one of the naturally occurring crystal forms of calcium carbonate (CaC0 3 ). Aragonite can exist in three crystal habits: acicular pyramidal, tabular, and
  • pseudohexagonal crystal habit leads to a hexagonal appearance.
  • US 2003/0180208 A1 discloses a process for preparation of precipitated aragonite, having a needle-like shape ('acicular aragonite'), with a thickness of a micron or less.
  • the precipitated aragonite can be used in applications in the prior art in which regular calcium carbonate is used.
  • JP 2002-180090 A discloses a silica-based compound consisting of an aggregate of acicular crystals, plate crystals or columnar crystals and having an average aggregate particle diameter of 0.5-500 micrometer.
  • WO 2009/040597 discloses a cleaning composition for hard surfaces, containing solid inorganic rnicroparticles having a particle size of from 0.5 to 5 micrometer, a surface area of from 10 to 50 m 2 /g and a crystallinity degree lower than 50 percent.
  • the inorganic rnicroparticles may be carbonates, and in one of the examples carbonate- substituted non-stoichiometric hydroxyapatite is used. These particles have the advantage that the abrasiveness has decreased.
  • US 2010/0263693 A1 discloses hard surface treatment compositions, wherein the particle size of an abrasive agent ranges from about 1 to 1000 micrometer, more preferably from about 10 to 100 micrometer.
  • Abrasive agents that will not scratch glass or ceramic surfaces are preferred, and these include calcium carbonate, siliceous chalk, diatomaceous earth, colloidal silicon dioxide, sodium metasilicate, talc, and organic abrasive materials.
  • WO 201 1/087733 A1 discloses a liquid cleaning composition comprising abrasive particles which have been defined based on roughness and hardness.
  • the abrasive particles preferably comprise polymeric particles, e.g. polyurethane.
  • the calcium carbonate forms used nowadays have the disadvantage that they contribute to the scratching of hard surfaces.
  • the present invention provides a liquid composition for cleaning of hard surfaces, comprising surfactant, and a particulate calcium carbonate abrasive composed of primary particles which are acicular and which have a length of
  • the level of the particulates ranges from 2 to 40% based on the total weight of the composition.
  • the present invention provides a method for cleaning of a hard surface, wherein a composition according to the first aspect of the invention is used.
  • the given range includes the mentioned endpoints.
  • the expressions 'soil' and 'stain' generally comprise all kinds of soils and stains generally encountered in the household, either of organic or inorganic origin, whether visible or invisible to the naked eye, including soiling solid debris and/or with bacteria or other pathogens.
  • a liquid composition refers to a composition that will flow under the force of gravity. This is in contradiction of pastes or gels, which keep their shape under the force of gravity.
  • calcium carbonate in liquid hard surface cleaners is well known.
  • the most common sources of calcium carbonate (CaC0 3 ) are rocks like limestone, chalk, marble, and travertine. The rock can be grinded into small or big pieces containing calcium carbonate.
  • Calcium carbonate can also be made and purified by a precipitation process. Precipitated calcium carbonate is usually produced by a series of chemical reactions. First step is conversion of limestone into calcium oxide and carbon dioxide by means of calcination at temperatures in excess of 900°C. Second step is slaking, wherein the calcium oxide reacts with with water, resulting into calcium hydroxide.
  • the resulting milk of lime is purified and carbonized with the carbon dioxide obtained from the calcination process, and calcium carbonate precipitates.
  • This precipitate may be concentrated by filtration, and the filter cake is then dried and subsequently disagglomerated in grinders.
  • the particle size, as well as the crystal form, is controlled by temperature, concentration of reactants and time.
  • a specific class of material suitable for use in the invention includes aragonite crystal form calcium carbonates such as those described for example in US 5, 164, 172.
  • aragonite crystal form calcium carbonate with an acicular shape is prepared by premixing aragonite calcium carbonate and Ca(OH) 2 to prepare an aqueous slurry, adding a water-soluble phosphoric acid compound (such as phosphoric acid or a water-soluble salt thereof) into the aqueous slurry, and introducing C0 2 gas into the aqueous slurry to cause a carbonation reaction to take place.
  • the molar ratio of the aragonite calcium carbonate to Ca(OH) 2 slurry is preferably 1 :7 to 1 :5000.
  • the resulting aragonite calcium carbonate crystals have an acicular shape and have a particle size of 10 to 100 micrometer (length) by 0.5 to
  • the length of the crystal ranges from 10 to 30 micrometer.
  • the ratio between the length and the width of a crystal is higher than 1 for acicular crystals.
  • the higher the aspect ratio the longer the crystal relative to the width.
  • the aspect ratio is preferably at least 2.5, more preferably at least 10.
  • the crystals are acicular aragonite with an aspect ratio ranging from 2.5 to 1000, preferably from 2.5 to 200, preferably from 10 to 100, and more preferably ranges from 10 to 60, and most preferably from 20 to 30.
  • the most preferred aragonite calcium carbonate crystals are rod-like or needle-like as described above, with a length ranging from 10 to 30 micrometer, a width ranging from 0.5 to 1.0 micrometer and an aspect ratio ranging from 20 to 30.
  • the cross-sectional shape of a crystal is not circular, then preferably the ratio between the longest and shortest dimensions of the cross-sectional shape, ranges from 1 : 0.2 to 1 : 1 , more preferably from 1 : 0.3 to 1 : 0.9, more preferred from 1 : 0.5 to 1 : 0.8.
  • Crystal morphology and structure may be determined by standard techniques known to those skilled in the art such as scanning electron microscopy (SEM).
  • SEM is an imaging and analysis technique based on the detection of electrons and X-rays that are emitted from a material when irradiated by a scanning electron beam. Imaging allows the user to distinguish between primary particle and agglomerate sizes.
  • phosphate ions and/or halophosphate ions leads to easier dosing of the composition, or even the possibility to spray the cleaning composition, while still having a good abrasive power.
  • high concentrations of calcium carbonate will lead to thick, highly viscous compositions that may be difficult to dose.
  • the amount of calcium carbonate abrasive can be increased to increase the abrasive strength of the composition, while the viscosity of the composition is not increased (which would make it more difficult to handle).
  • the total concentration of calcium carbonate abrasives preferably ranges from 15 to 40% by weight of the composition, preferably from 18 to 30% by weight, preferably from 20 to 25% by weight of the composition.
  • the composition of the invention preferably comprises ground calcium carbonate in the form of calcite crystals.
  • the most commonly used calcium carbonate abrasive in the compositions of the prior art is calcium carbonate in the form of calcite, that is obtained by grinding natural calcium carbonate.
  • this ground calcium carbonate in the form of calcite crystals have a largest dimension ranging from 20 micrometer tp
  • the amount of particulate calcium carbonate abrasive composed of primary particles which are acicular is at least 50 wt% of the total amount of calcium carbonate, preferably at least 75 wt%. Hence preferably at least half or even most of the calcium carbonate present is in the form of the acicular calcium carbonate of the invention.
  • More preferred at least 75% of the calcium carbonate present is in the form of the acicular calcium carbonate of the invention.
  • the particulate precipitated calcium carbonate with a calcite crystal structure comprises a crystal having a calcite prismatic crystal structure.
  • the particulate precipitated calcium carbonate with a calcite crystal structure has a prismatic crystal structure, with a largest dimension ranging from 0.1 to
  • the particle size distribution is such that at least 50% of the particles has a size smaller than
  • At least half or even most of the calcium carbonate present is in the form of the acicular calcium carbonate of the invention. More preferred at least 75% of the calcium carbonate present is in the form of the acicular calcium carbonate of the invention.
  • the particulate precipitated calcium carbonate with a calcite crystal structure comprises a crystal having a calcite scalenohedral crystal structure.
  • the particulate precipitated calcium carbonate with a calcite crystal structure has a scalenohedral crystal structure, and wherein the crystals are
  • the agglomerate has a largest dimension ranging from 1 to 20 micrometer, preferably from 2 to 15 micrometer.
  • the particle size distribution is such that at least 50% of the particles has a size smaller than
  • the primary particles from which the agglomerates are made preferably have a largest dimension of maximally 1 micrometer.
  • at least half or even most of the calcium carbonate present is in the form of the acicular calcium carbonate of the invention. More preferred at least 75% of the calcium carbonate present is in the form of the acicular calcium carbonate of the invention.
  • the compositon of the invention may contain in addition to the abrasive acicular calcium carbonate, a combination of precipitated calcium carbonate with a calcite prismatic crystal structure and precipitated calcium carbonate having a calcite scalenohedral crystal structure.
  • the weight ratio of the two forms ranges from 5:1 to 1 :5.
  • the liquid cleaning composition of the invention comprises a surfactant, preferably at a concentration of maximally 50% by weight of the composition.
  • the surfactant preferably at a concentration of maximally 50% by weight of the composition.
  • detergent active is generally chosen from anionic and nonionic detergent actives.
  • the cleaning composition may further comprise cationic, amphoteric and zwitterionic surfactants.
  • the total amount of surfactant the cleaning composition is at least 0.1 %, more preferably at least 0.5%.
  • the maximum amount is usually less than 30%, more preferably not more than 20%, or even at or below 10% by weight.
  • Suitable synthetic (non-soap) anionic surfactants are water-soluble salts of organic sulphuric acid mono-esters and sulphonic acids which have in the molecular structure a branched or straight chain alkyi group containing from 6 to 22 carbon atoms in the alkyi part.
  • anionic surfactants are water soluble salts of:
  • PAS primary alcohol sulphates
  • alkyi benzene sulphonates such as those in which the alkyi group contains from 6 to 20 carbon atoms;
  • alkylglyceryl ether sulphates especially of the ethers of fatty alcohols derived from tallow and coconut oil;
  • alkylphenol ethylenoxy-ether sulphates with from 1 to 8 ethyleneoxy units per molecule and in which the alkyi groups contain from 4 to 14 carbon atoms;
  • the preferred water-soluble synthetic anionic surfactants are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of alkyl-benzenesulphonates and mixtures with olefinsulphonates and alkyl sulphates, and the fatty acid mono-glyceride sulphates.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonat.es containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonat.es or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-sulphonate, and sodium dinonyl-naphthalene-sulphonate.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonat.es containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonat.es or of alkyl-toluene-, -xylene- or -phenols
  • the amount present in the cleaning compositions of the invention will generally be at least 0.1 %, preferably at least 0.5%, more preferably at least 1 .0%, but not more than 20%, preferably at most 15%, more preferably at most 10%.
  • a suitable class of nonionic surfactants can be broadly described as compounds produced by the condensation of simple alkylene oxides, which are hydrophilic in nature, with an aliphatic or alkyl-aromatic hydrophobic compound having a reactive hydrogen atom.
  • the length of the hydrophilic or polyoxyalkylene chain which is attached to any particular hydrophobic group can be readily adjusted to yield a compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB.
  • Particular examples include:
  • condensates of the reaction product of ethylene-diamine and propylene oxide with ethylene oxide the condensates containing from 40 to 80% of ethyleneoxy groups by weight and having a molecular weight of from 5,000 to 1 1 ,000.
  • Other classes of nonionic surfactants are: tertiary amine oxides of structure R 1 R 2 R 3 N-0, where R 1 is an alkyl group of 8 to 20 carbon atoms and R 2 and R 3 are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, e.g. dimethyldodecylamine oxide;
  • R 1 R 2 R 3 P-0 tertiary phosphine oxides of structure R 1 R 2 R 3 P-0, where R 1 is an alkyl group of 8 to 20 carbon atoms and R 2 and R 3 are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide;
  • dialkyl sulphoxides of structure R 1 R 2 S 0, where R 1 is an alkyl group of from 10 to 18 carbon atoms and R 2 is methyl or ethyl, for instance methyl-tetradecyl sulphoxide;
  • fatty acid alkylolamides such as the ethanol amides
  • the concentration of the nonionic surfactant preferably employed in the cleaning composition of the invention will preferably be at least 0.1 %, more preferably at least 0.5%, most preferably at least 1 %.
  • the amount is suitably at most 20%, preferably not more than 15% and most preferably not more than 10%.
  • Suitable cationic surfactants can be found among quaternary ammonium salts having one or two alkyl or aralkyl groups of from 8 to 20 carbon atoms and two or three small aliphatic (e.g. methyl) groups, for instance cetyltnmethylammonium chloride.
  • a specific group of surfactants are the tertiary amines obtained by condensation of ethylene and/or propylene oxide with long chain aliphatic amines. The compounds behave like nonionic surfactants in alkaline medium and like cationic surfactants in acid medium.
  • Suitable zwitterionic surfactants can be found among derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance betaine and betaine derivatives such as alkyl betaine, in particular Ci 2 -Ci 6 alkyl betaine, 3-(N,N-dimethyl-N- hexadecylammonium)-propane-1 -sulphonate betaine, 3-(dodecylmethyl-sulphonium)- propane-1-sulphonate betaine, 3-(cetylmethyl-phosphonium)-propane-1-sulphonate betaine and N,N-dimethyl-N-dodecyl-glycine.
  • betaines are the alkylamidopropyl betaines e.g. those wherein the alkylamido group is e
  • surfactants are compounds commonly used as surface- active agents given in the well-known textbooks: 'Surface Active Agents' Vol.1 , by Schwartz & Perry, Interscience 1949; 'Surface Active Agents' Vol.2 by Schwartz, Perry & Berch, Interscience 1958; the current edition of 'McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company; Tenside- Taschenbuch', H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
  • the pH of the composition according to the invention preferably ranges from 7 to 12, more preferably from 8 to 1 1 , most preferred from 9 to 1 1.
  • the pH of the cleaning composition of the invention may be adjusted with organic or inorganic acids or bases.
  • Preferred inorganic bases are preferably alkali or alkaline earth hydroxides, ammonia, or bicarbonates, the alkali metal preferably being sodium or potassium or the alkaline earth metal preferably being calcium or magnesium.
  • the organic bases are preferably amines, alkanolamines and other suitable amino compounds.
  • Inorganic acids may include hydrochloric acid, sulphuric acid or phosphoric acid, and organic acids may include acetic acid, citric acid or formic acid as well as dicarboxylic acid mixtures such as Radimix (trade mark, Radici Group) and Sokalan DCS (trade mark, BASF).
  • compositions may contain other ingredients which aid in their cleaning
  • compositions used according to the invention may contain detergent builders and mixtures of builders in an amount of up to 25%, in particular when the composition contains one or more anionic surfactants. If present, the builder preferably will form at least 0.1 % of the cleaning composition. Suitable inorganic and organic builders are well known to those skilled in the art.
  • a further optional ingredient for compositions used according to the invention is a suds regulating material, which can be employed in compositions which have a tendency to produce excessive suds in use. Examples thereof are fatty acids or their salts (soap), isoparaffins, silicone oils and combinations thereof.
  • Soaps are salts of fatty acids and include alkali metal soaps such as the sodium, potassium and ammonium salts of fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms. Particularly useful are the sodium and potassium and mono-, di- and triethanolamine salts of the mixtures of fatty acids derived from palm oil, coconut oil and ground nut oil. When employed, the amount of fatty acid or soap can form at least 0.005%, preferably 0.1 % to 2% by weight of the composition.
  • hydrocarbon solvent is present at a sufficiently high level this may itself provide some or all of the required antifoaming activity.
  • Compositions may also contain, in addition to the ingredients already mentioned, various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), solvents, co-solvents, gel-control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example 1 ,2-benzisothiazolin-3-one), hydrotropes and perfumes.
  • various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly peroxide compounds and active chlorine releasing compounds), solvents, co-solvents, gel-control agents, further freeze-thaw stabilisers, bactericides, preservatives (for example 1 ,2-benzisothiazolin-3-one), hydrotropes and perfumes.
  • the liquid composition of the invention may be stored in and dispensed by any suitable means, but spray applicators are particularly preferred. Pump dispensers (whether spray or non-spray pumps) and pouring applicators (bottles etc.) are also possible.
  • the composition of the invention is comprised in a container, wherein the container comprises a spray dispenser for dispensing the composition in the form of a spray.
  • the spray dispenser is preferably a trigger spray but may be any suitable means.
  • the present invention provides A method for cleaning of a hard surface, wherein a composition according to the first aspect of the invention is used.
  • the method of the invention can be employed by the person skilled in the art.
  • the result of the method is that a hard surface is easily cleaned without damage to the surface, as facilitated by the composition of the invention.
  • the composition is sprayed onto the surface using a spray dispenser.
  • Figure 1 Top: Scanning electron microscopy image (ruler width is 10 micrometer) and typical size indication of Whiscal® calcium carbonate rods (see Table 1 );
  • Figure 3 Scanning electron microscopy image (ruler width is 10 micrometer) of Socal S2E (see Table 1 ); with determination of typical size of crystals.
  • Figure 4 Scanning electron microscopy pictures of various types of acicular calcium carbonate crystals (see Table 4 in example 2).
  • Figure 7 Photographs of perspex surface, from example 4.
  • liquid abrasive cleaner as described in Table 2
  • the soil is prepared from calcium stearate, carbon black, and propan-2-ol (in a weight ratio of about 0.17:0.003:1 ), applied to the tile and baked in an oven at 180°C for 35 minutes.
  • liquid abrasive cleaner as described in Table 2
  • a damp cloth 'Ballerina', ex Unilever
  • a linear scrubbing device Erichsen
  • Three different head weights ('low', 'medium', 'high') are used in this analysis, respectively, to assess the different levels of damage cause by increased pressure.
  • 'Low' no addition weight is added to the scrubbing head.
  • 'Heavy' a second weight is added to the scrubbing head giving a total additional weight of 1 ,327 g.
  • the maximum pressure to be used is 80 g.cm "2 .
  • the following pressure ranges are employed, respectively for the heads: 5-20 g.cm “2 , 15- 50 g.cm “2 , and 25-80 g.cm “2 .
  • the perspex is measured over 7 points with a gloss meter before and after scrubbing to assess the loss of gloss to the surface. These measurements are carried out at 20° and 60° (reflectance angles at which the gloss is measured) and presented as a percentage loss of gloss. An angle of 20° is most relevant for a shiny surface.
  • the pre-screening of raw materials for abrasion is done with an abrasion testing machine (Abrasion Tester AT2010, Leaderpower, China), and the number of revolutions is set at 87,000.
  • Pre-treatment of screen Prepare 250 ml 0.5 wt% Alconox solution (Concentrated, anionic detergent, ex Alconox (White Plains, NY, USA), in sonic bath for 1 minute. Then put copper screen in the solution and sonicate for 5 minutes. Rinse the screen under hot running tap water for 3 minutes, holding with tweezer. Put the screen in distilled water and sonicate for 5 minutes, and 3 minutes more in distilled water. Heat the screen at 105°C for 20 minutes and cool down in a desiccator. Weigh the screen on
  • the copper screen is put at the bottom of fully dispersed raw material slurry (10.0 g of material in 90.0 g of water) and rubbed with PVC tube. After the testing, rinse the screen under hot running water until visible debris is removed. Then wash it with distilled water in sonic bath for 2 minutes, and 2 more minutes with running distilled water. At last, heat it at 105°C for 20 minutes and cool down in a desiccator. Re-weigh the screen and record the data as W a f ter .
  • Whiscal whisker-shaped calcium carbonate
  • precipitated calcium carbonate ex Maruo Calcium Company Ltd. (Akasi, Hyogo, Japan)
  • particle size distribution 80 wt% ⁇ 3 micrometer (equivalent spherical diameter), 60 wt% ⁇ -2.3 micrometer, 40 wt% ⁇ 2 micrometer, 20 wt% ⁇ -1.2 micrometer.
  • premix made in house 19.675 First the premix is made, involving reacting LAS Acid with caustic soda to produce anionic surfactant. The premix is mixed with the other ingredients of the main mix.
  • Example 1 Testing acicular calcium carbonate
  • Table 3 Combinations of calcium carbonate abrasives used in the composition of Table 2, results on cleaning (1, 3, or 5 lissajous), damage (using 3 weights), and ratio between cleaning and damage.
  • the (fictive) ratio between cleaning and damage is a measure for the relation between cleaning and damage: a high value of this number gives a good cleaning result and little damage, while a low value indicates that either the cleaning performance decreases or the damage increases high, or both.
  • Table 4 Sources of various types acicular calcium carbonate rods, all precipitated calcium carbonate.
  • Rods 1 were obtained from the supplier.
  • the properties of rods 2 to 7 were determined by counting 50 rods from a scanning electron microscopy image.
  • Step 1 Controlled stress steps from 0.01 to 400 Pa; 40 steps logarithmically spaced in stress with 40 s being spent at each point to measure the shear rate (and hence viscosity); Step 1 is terminated once a shear rate of 0.1 s "1 is reached.
  • Step 2 Controlled shear rate steps from 0.1 to 1200 s "1 ; 40 steps
  • Step 3 Controlled shear rate steps from 1200 to 0.1 s "1 ; 40 steps
  • the rheology is described in terms of the pouring viscosity (in Pa.s) at a shear rate of 21 s "1 and the yield stress of the system in Pa.
  • the yield stress is taken to be the value of the stress at a shear rate of 0.1 s '
  • the yield stress indicates at which stress the material starts to deform plastically (the yield point), i.e. it flows as a liquid. At lower stress values than the yield stress (prior to the yield point) the material will deform elastically and will return to its original shape when the applied stress is removed. Once the yield point is passed, some fraction of the deformation will be permanent and nonreversible.
  • composition in Table 2 was prepared for each calcium carbonate rods in Table 4, as well for the reference.
  • the highest yield stress is obtained for the product containing the Whiscal rods. This product also has the highest viscosity when pouring. The product with the highest yield stress has the best ability to suspend a dispersed phase (i.e. denser or bigger particles). These pouring viscosities determine how easy it is to pour or squeeze the product from a packaging material. Practically the ease of squeeze is dominated by the stiffness of the packaging. Table 7 Results of cleaning (1, 3, or 5 lissajous), damage (using 3 weights), and ratio between cleaning and damage of compositions from Table 2 containing various types acicular calcium carbonate rods
  • the (fictive) ratio between cleaning and damage is a measure for the relation between cleaning and damage: a high value of this number gives a good cleaning result and little damage, while a low value indicates that either the cleaning performance decreases or the damage increases high, or both.
  • the reference sample prior art composition with Omyacarb
  • the results should be compared between the same number of lissajous. In this case all rods have a higher value than the comparative example. Especially the rods 1 and 5 show good results. These rods have a width generally less than 1 micrometer.
  • Example 3 Liquid abrasive cleaner with phosphate or fluorophosphate ions
  • TSP Trisodium phosphate dodecahydrate
  • SMFP monofluorophosphate
  • CaC0 3 rods are mixed with 60g water while stirring.
  • additives SMFP or Na 3 P0 4 were added into the mixture while stirring.
  • concentrated NaOH solution (10 mol/L) was added into the mixture drop by drop until the pH reaches about 10. The mixture is stirred for 10 minutes.
  • Rheology was determined using a rheometer Physica MCR 301 (Anton Paar, Austria), at variable shear rate (0.001 -1000 s "1 ), geometry: PP50/TG SN6884, profile: ram log.
  • Table 9 Compositions of formulations for rheology measurements, rheology data in Figure 6.
  • the data show that the addition of phosphate ions or fluorophosphate ions leads to a lower viscosity of the formulation containing calcium carbonate rods, especially at a shear rate smaller than about 10 s "1 .
  • the effect is shown both at pH 7 and pH 10.
  • a composition can be made, that has a relatively high content of calcium carbonate for abrasive cleaning, that does not strongly damage the hard surface, and that has a relatively low viscosity, as compared to a composition without the phosphate ions.
  • Example 4 Polishing effect of the particulate calcium carbonate abrasive
  • FIG. 7 shows photographs of the surface of the perspex before and after rubbing with the compositions. These pictures indeed show that the before rubbing the surface of the perspex is smooth and shiny (left). After rubbing with the conventional composition, many scratches are visible, the surface seems to have become more grey than black (middle picture). After the rubbing with the composition with the rods, the perspex surface has become smooth and black again (right picture), clearly a polishing effect.

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  • Chemical Kinetics & Catalysis (AREA)
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PCT/CN2012/084669 2011-12-01 2012-11-15 Liquid composition for cleaning of head surfaces WO2013078949A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
IN943MUN2014 IN2014MN00943A (xx) 2011-12-01 2012-11-15
EP12853510.1A EP2785822A4 (en) 2011-12-01 2012-11-15 LIQUID COMPOSITION FOR CLEANING HARD SURFACES
ZA2014/03699A ZA201403699B (en) 2011-12-01 2014-05-21 Liquid composition for cleaning of head surfaces

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CNPCT/CN2011/002010 2011-12-01
CN2011002010 2011-12-01
EP12151396.4 2012-01-17
EP12151396 2012-01-17

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EP2865740A1 (de) * 2013-10-24 2015-04-29 Werner & Mertz GmbH Flüssiges Scheuermittel
EP2216306B1 (de) 2009-02-06 2015-08-19 STO SE & Co. KGaA Viskose, kornhaltige aushärtende beschichtungsmasse
EP3045503A1 (en) 2015-01-15 2016-07-20 Omya International AG Surface-treated calcium carbonate with improved stability in environments with a pH of 4.5 to 7
US10780031B2 (en) 2013-12-13 2020-09-22 Omya International Ag Abrasive cleaning composition
WO2020153929A3 (en) * 2019-01-23 2020-09-24 Abc Deterjan Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ New generation liquid cream cleaning compound and production method

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2216306B1 (de) 2009-02-06 2015-08-19 STO SE & Co. KGaA Viskose, kornhaltige aushärtende beschichtungsmasse
EP2216306B2 (de) † 2009-02-06 2021-06-02 STO SE & Co. KGaA Viskose, kornhaltige aushärtende beschichtungsmasse
EP2865740A1 (de) * 2013-10-24 2015-04-29 Werner & Mertz GmbH Flüssiges Scheuermittel
US10780031B2 (en) 2013-12-13 2020-09-22 Omya International Ag Abrasive cleaning composition
EP3045503A1 (en) 2015-01-15 2016-07-20 Omya International AG Surface-treated calcium carbonate with improved stability in environments with a pH of 4.5 to 7
WO2016113285A1 (en) 2015-01-15 2016-07-21 Omya International Ag Surface-treated calcium carbonate with improved stability in environments with a ph of 4.5 to 7
WO2020153929A3 (en) * 2019-01-23 2020-09-24 Abc Deterjan Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ New generation liquid cream cleaning compound and production method

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IN2014MN00943A (xx) 2015-04-24
ZA201403699B (en) 2015-11-25
EP2785822A1 (en) 2014-10-08
EP2785822A4 (en) 2015-12-16

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