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EP1235895B1 - Utilisation de matiere polymere dans le traitement de surfaces dures - Google Patents

Utilisation de matiere polymere dans le traitement de surfaces dures Download PDF

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Publication number
EP1235895B1
EP1235895B1 EP00993324A EP00993324A EP1235895B1 EP 1235895 B1 EP1235895 B1 EP 1235895B1 EP 00993324 A EP00993324 A EP 00993324A EP 00993324 A EP00993324 A EP 00993324A EP 1235895 B1 EP1235895 B1 EP 1235895B1
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EP
European Patent Office
Prior art keywords
polymeric material
polymer
use according
nucleation
hard surface
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.)
Revoked
Application number
EP00993324A
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German (de)
English (en)
Other versions
EP1235895A1 (fr
Inventor
A.T. Unilever Research Port Sunlight ASHCROFT
Melvin Unilever Research Port Sunlight CARVELL
K.M. Unilever Research Port Sunlight HUMPREYS
Ezat Unilever Research Port Sunlight KHOSDEL
Xiang Yang National University of Singapore LIU
Steven Unilever Research Port Sunlight RANNARD
Andrew Mark Unilever NV WALLER
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to ES00993324T priority Critical patent/ES2304360T3/es
Priority to EP00993324A priority patent/EP1235895B1/fr
Publication of EP1235895A1 publication Critical patent/EP1235895A1/fr
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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular 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
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to the use of polymeric material in the treatment of hard surfaces to deal with scale forming calcium salts.
  • Scale is an important soil in bathrooms and kitchens and one which is not easy to remove.
  • Household water supplies contain varying levels of calcium and magnesium salts. Residual water left after, e.g. bathing, showering, dishwashing, rinsing, etc. will eventually evaporate leading to the deposition of calcium salts on surfaces as scale.
  • the scale deposits formed can become unsightly, hard and very difficult to remove. This can happen particularly quickly in hard water areas where the level of calcium in domestic water is high.
  • Conventional hard surface cleaners may comprise acid or abrasive in order to assist with the removal of scale.
  • enamel and marble surfaces are susceptible to acid damage and all surfaces may become scratched and unsightly due to the excessive use of abrasive.
  • WO 99/60086 discloses acidic compositions comprising polyvinylpyrrolidone and a polysaccharaide such as xanthan.
  • the compositions provide a next-time cleaning benefit and are said to reduce or prevent the formation of limescale.
  • no data are given to support this claim.
  • EP 0 875 555 discloses acidic compositions comprising a polysaccharide such as xanthan. Again the compositions provide a next-time cleaning benefit and are said to reduce or prevent the formation of limescale, but again, no data are given to support this claim.
  • the present inventors have realised that, whereas it may not be possible to prevent deposition of calcium salts, it will be possible to control the mechanism of calcium salt deposition and thereby affect the strength of bond between calcium salts and the hard surface.
  • a polymeric material can be deposited onto a hard surface to inhibit heterogeneous nucleation at that surface. The majority of the nucleation will then occur in the bulk solution leading to the deposition of scale forming salts that are easy to remove.
  • the polymer also reduces further aggregation and toughening of new scale on already existing scale deposits.
  • Preventing scale from forming or adhering to household surfaces will retain the smoothness of the surface and prevent it from dulling. This is particularly important for surfaces which are likely to come in extensive contact with water such as can be found in bathrooms, toilets, kitchens and the like. Such surfaces are often made of metal, vitreous materials or hard plastics.
  • the present invention accordingly provides the use of a polymeric material to reduce heterogeneous nucleation of calcium and magnesium salts at hard surfaces comprising depositing onto the hard surface, a polymeric material which is a natural polymer modified with nitrogen containing species and wherein furthermore the polymeric material has a weight average molecular weight greater than 10,000 and has cationic groups or groups which become cationic at the pH of use.
  • the invention also provides a process for preventing scale from forming or adhering to metal, vitreous or hard plastic surfaces comprising applying to the surface a cleaning composition comprising a detergent surfactant and a polymeric material as described above
  • polymeric material are suitable for use in the present invention. It is required that the polymer is one which, when deposited onto a hard surface at a suitable level, will reduce heterogeneous nucleation of scale forming salts at that surface. Preferably, polymeric material achieves a reduction in the nucleation rate (number of nuclei per unit area per unit time) of scale forming salts at the surface. The following test has been derived to determine whether a polymeric material achieves a reduction in nucleation density (number of nuclei per unit area), which can easily be converted into a nucleation rate if the duration of the experiment is also recorded.
  • the test comprises applying a solution of polymer of known concentration to a first area sample of a hard surface, providing a second area sample of the hard surface having no polymer thereon and flowing a supersaturated solution of a scale forming salt over each area sample of the hard surface for a known period of time and comparing the number of nuclei formed per unit area per unit time for the area sample treated with the polymeric material with the number of scale nuclei formed per unit area per unit time for the untreated area sample to obtain an estimate of the reduction of the rate of heterogeneous nucleation at the hard surface.
  • All tubing used in the apparatus comprises PTFE tubing for example OD 3.2 mm, ID 1.5 mm obtainable from Omnifit (Trade Mark).
  • the apparatus is jacketed in nitrogen to ensure that carbon dioxide is not reabsorbed.
  • the mixing cell 5 comprises a block of PTFE which has a hollow spherical space 7 formed in its interior.
  • the spherical space 7 is of volume 1 mm 3 .
  • Projecting through the block and into the space 7 are two capillary tubes, 8 and 9 along which solutions A and B are delivered respectively.
  • the capillary tubes 8 and 9 terminate in nozzles close to the centre of the hollow space 7.
  • the solutions A and B are directed towards one another and mixed in the centre of the hollow space 7.
  • the resulting mixed solution leaves the hollow space 7 through a duct 10, whence it is delivered to the experimental surface to be tested.
  • the capillaries 8 and 9 have end openings of 100 micrometres diameter.
  • the mixture of solutions is directed onto a surface to be tested.
  • the surface 11 to be tested is mounted beneath a nozzle 12, through which the mixed solution from the mixing cell 5 is delivered to the surface 11.
  • the resulting flow pattern is a wall-jet flow pattern, which is well understood by the person skilled in the art.
  • the flow is radially outwards from the centre of the surface 11 to be tested, and is uniform.
  • the nozzle 12 is a 0.8 mm internal diameter PTFE nozzle placed 3 mm above the surface 11.
  • the mixed solution is delivered at a flow rate of 4 cm 3 /min.
  • the wall jet apparatus 6 is jacketed in nitrogen to prevent CO 2 absorption.
  • the apparatus allows continual refreshment of the surface with solution of known composition allowing crystal growth to occur under conditions of constant supersaturation.
  • the apparatus is used to test a surface by the following method.
  • a supersaturated solution is created in a manner known to the person skilled in the art by mixing together two stable, undersaturated solutions.
  • the solutions are degassed before use using N 2 to remove dissolved CO 2 .
  • Solution is flowed over the surface to be treated for a fixed time.
  • a suitable time is 45 minutes.
  • scale forming salt is deposited onto the surface.
  • any crystals at the air/water interface are suctioned away using a small piece of tubing attached to a water pump.
  • the surface is then removed from the apparatus 6, rinsed briefly with a saturated solution of the scale forming salt, dried with nitrogen and inspected under a microscope.
  • Characterisation of the degree of crystal growth on a surface to be tested can be achieved using a digitised map of the surface produced by micrographics. This map may then be processed using image analysis software (for example Aequitas, Dynamic Data Links Ltd) which allows automated measurements of crystal size, number and distribution over a choice of area. This allows the nucleation density to be measured.
  • image analysis software for example Aequitas, Dynamic Data Links Ltd
  • the surfaces to be tested can be prepared and treated in any way as long as the surface remains reasonably flat.
  • Sample surfaces are preferably polished to a finish of 1/20 micrometres using 0.05 gamma alumina obtainable from Buehler.
  • half of the surface is masked and half is treated with a solution or dispersion of the polymeric material.
  • a 50 microlitre drop of the polymer solution is placed onto the unmasked half of the sample surface and allowed to wet that part of the surface. The drop is left until dry and washed with 10 sprays of deionised water from a trigger spray gun. Drying time may be from 5 minutes to 20 hours, as appropriate.
  • the surface 11 to be tested is in the form of a disc.
  • a set of discs of the same size consisting of a stainless steel disc, a ceramic disc, an enamel coated disc, a glass disc and a perspex disc.
  • the nucleation density on the untreated half can then be compared to the nucleation density on the treated half.
  • the experiment may be repeated with different types of calcium salt, for example, calcium carbonate or calcium sulphate or with magnesium salts such as magnesium carbonate or magnesium sulphate.
  • Polymers which are particularly suitable for use in the present invention reduce the nucleation density at the surface by at least 10% on at least one of the test surfaces (glass, steel, ceramic, enamel or perspex) with at least one of the salts (calcium carbonate, calcium sulphate, magnesium sulphate, magnesium carbonate). More preferably the polymer will reduce the nucleation rate by at least 20%, even more preferably by at least 30% and most preferably by at least 50%.
  • the polymer should achieve a reduction in nucleation density of at least 10%, more preferably at least 20% with both calcium carbonate and calcium sulphate, on any one of the surfaces, more preferably on both of steel and glass and most preferably on all of steel, glass, ceramic and enamel.
  • the contact angle is a manifestation of the surface energy at the interface between water and the polymer-treated surface which in turn determines the degree to which developing scale crystal nuclei are bonded to the surface. It appears this bonding is strongest for surfaces causing the contact angle to be between 30° and 60°
  • the contact angle made by a drop of water on the treated steel surface can be measured by any of the commonly known methods.
  • the measurements can be made using a travelling microscope with a simple goniometer head, in which the eyepiece is fitted with crosshairs.
  • a 20 ⁇ l drop of water is pipetted onto the horizontal treated steel surface.
  • the crosshairs in the microscope eyepiece are aligned such that the horizontal mark is aligned with the steel surface (i.e., along the steel/water interface).
  • the centre of the cross is aligned with the three phase contact point (i.e., the water/steel/air interface).
  • the crosshairs are then rotated to align with the edge of the water drop (i.e., along the air/water interface)and the resulting angle is read off on the goniometer scale.
  • Polymers for use in the present invention preferably deposit well onto hard surfaces. They may be applied in any way known in the art. Preferably they are applied in the form of a liquid composition containing the polymer in solution or dispersion. More preferably such compositions are aqueous liquids.
  • compositions containing the polymers for use in the present invention may be applied in a number of ways, as will be discussed below. For example, they may be applied to a surface and left in contact to evaporate to dryness. In this case, it is simply required that the polymer should be capable of forming a thin and smooth layer, suitably of the order of a few molecular layers of submicron thickness. Other compositions may be applied to the surface with the intention of the surface being subsequently wiped dry. In such cases, it is preferable that the polymer should also have an increased tendency to adsorb to the hard surface.
  • compositions containing the polymers are cleaning compositions which have the additional effect of depositing a polymer for inhibiting nucleation at the surface to be treated.
  • Such compositions will normally contain one or more detergent surfactants in addition to the polymer.
  • the polymer has activity at the solid/liquid interface. It is particularly preferred that the polymer should adhere sufficiently strongly to the surface to be resistant to removal by rinsing. However, the polymer should not adhere too strongly to the surface, otherwise there may be a tendency for the polymer to build up on the surface which might lead to negative effects, e.g. poor appearance.
  • the polymer should have cationic groups or groups which become cationic at the pH of use. It is preferred that the polymer should comprise amine groups, particularly quaternary ammonium or tertiary amine groups.
  • Deposition of the polymer may also be assisted if it has a relatively high molecular weight.
  • the weight average molecular weight is greater than 10,000, preferably greater than 50,000.
  • Deposition of the polymer may also be assisted if the polymer or a complex of the polymer with a surfactant is rigid or semi-rigid.
  • the polymeric material may have an inflexible backbone e.g. due to unsaturation or the presence of rings. Alternatively, it may have a positive charge, either permanently or temporarily at the pH of the composition, restricting conformation of the backbone due to repulsion between charges, or it may have a backbone which is flexible in principle but restricted in molecular conformation derived from polymer architecture, e.g. branching, unsaturation, rings or bulky side groups.
  • deposition of the polymer may also be encouraged by the use of a deposition aid such as a cationically charged polymer or surfactant.
  • the polymeric material has at least one of the following properties:
  • Polymeric materials for use in the present invention are preferably soluble or dispersible in surfactant solution but difficultly soluble or dispersible in water.
  • the polymeric material may also be partially water-soluble and soluble in aqueous surfactant solution of the type used in hard surface cleaning compositions.
  • the solubility of the polymeric material in an aqueous surfactant solution is suitably in the range of 0.01-50% by weight, more preferably in the range 0.05-10%, most preferably around 0.1-1.0%, particularly 0.4-1.0% by weight.
  • the surfactant concentration is suitably in the range 0.1-20% by weight, preferably 1.0-10% or 6% by weight.
  • the present application may be carried out with many types of polymer of suitable structure to achieve the properties described above.
  • the following non-limiting examples may be given.
  • Polymers suitable for use in the present invention may be produced by any suitable polymerisation method, for example emulsion or solution polymerisation.
  • Copolymers may for example be produced by graft, block or bulk copolymerisation.
  • Hydrophobicity may be introduced into polymers for example by including hydrophobic side chains, such as C 8 -C 22 alkyl, alkenyl or alkylaryl chains. These can be introduced for example as esters of C 8 -C 22 alcohols or the like.
  • Polymers which are used in the present invention comprise natural polymers, such as starches and gums, modified with nitrogen containing species.
  • the polymer may comprise guar gum, cellulose, locust bean gum, starch, starch amylose or similar natural polymers.
  • the natural polymer may be modified by reaction of the hydroxyl groups with other groups, to provide side groups to modify the substantivity of the polymer surface or to provide nucleation inhibiting effects.
  • the natural polymer may be modified with nitrogen containing species such as hydroxypropyltrimethylammonium groups.
  • the polymers may comprise cationic guar gums such as hydroxypropyltrimethylammonium guar gum with a degree of substitution in the range 0.11 to 0.22, available commercially under the trade marks JAGUAR C13S, JAGUAR C14S, JAGUAR C17 and JAGUAR C-162.
  • polyquaternary polymers such as Polyquat 10 which is commercially available under the trademarks Polymer JR30M, JR125 and JR400.
  • Hydrophobicity may be provided by modifying the natural polymer with, for example, hydrophobic substituents such as C 8 -C 22 alkyl chains, tertiary alkyl groups etc.
  • the polymeric material is not highly coloured across the pH range of interest (3-12).
  • the polymeric material can be used according to the present invention in any suitable formulation.
  • the formulation must be suitable for depositing the polymeric material onto a hard surface.
  • the polymeric material may be present in the formulation in any suitable form, for example in the form of a solution or dispersion.
  • Suitable formulations include solutions, dispersions or emulsions of the polymeric material in a carrier, for example a substantially non-aqueous material such as ethanol, but preferably water.
  • a carrier for example a substantially non-aqueous material such as ethanol, but preferably water.
  • the compositions may be used only to deposit polymeric material, or they may have additional functions such as cleaning.
  • composition may be applied by any suitable means.
  • it can be poured or sprayed onto the surface from a container or from an aerosol can or from a spray gun applicator.
  • compositions for use in the present invention may include any normal ingredients for hard surface cleaning compositions.
  • a hard surface cleaning composition comprises at least one detergent surfactant and optional other hard surface cleaning components.
  • composition according to the invention will comprise detergent actives (surfactants) which are generally chosen from both anionic and nonionic detergent actives.
  • Suitable anionic surfactants are water-soluble salts of organic sulphuric acid esters and sulphonic acids which have in the molecular structure an alkyl group containing from 8 to 22 carbon atoms.
  • anionic surfactants water soluble salts of:
  • 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 alkylbenzenesulphonates and mixtures with olefinsulphonates and alkyl sulphates, and the fatty acid mono-glyceride sulphates.
  • the most preferred anionic surfactants are alkylaromatic sulphonates such as alkylbenzenesulphonates 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 alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-sulphonate, and sodium dinonylnaphthalene-sulphonate.
  • alkylaromatic sulphonates such as alkylbenzenesulphonates 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 alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkyln
  • the amount present in the compositions of the invention will generally be at least 0.5%, preferably at least 1.0%, more preferably at least 2.0%, but not more than 20%, preferably at most 10%, more preferably at most 8%
  • Suitable nonionic 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 attached to any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB, taking into account the presence of the organic solvent and possible hydrocarbon cosolvent in the composition.
  • 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 condensates 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 condensates containing from 40 to 80% of ethyleneoxy groups by weight and having a molecular weight of from 5,000 to 11,000.
  • Alkylglycosides which are condensation products of long chain aliphatic alcohols and saccharides
  • tertiary amine oxides of structure RRRN0 where one R is an alkyl group of 8 to 18 carbon atoms and the other Rs are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyldodecylamine oxide
  • tertiary phosphine oxides of structure RRRP0 where one R is an alkyl group of 8 to 18 carbon atoms and the other Rs are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide
  • dialkyl sulphoxides of structure RRS0 where one R is an alkyl group of from 10 to 18 carbon atoms and the other is methyl or ethyl, for instance methyltetradecyl sulphoxide
  • fatty acid alkylolamides alkylene
  • the amount of nonionic surfactant to be employed in the cleaning composition of the invention will preferably be at least 0.2%, more preferably at least 0.5%, most preferably at least 1%.
  • the maximum amount is suitably 15%, preferably 10% and most preferably 70.
  • compositions may contain amounts of both anionic and nonionic surfactants which are chosen, bearing in mind the level of electrolyte present, so as to provide a structured liquid detergent composition, i.e. one which is 'self-thickened'.
  • a structured liquid detergent composition i.e. one which is 'self-thickened'.
  • the weight ratio of anionic surfactant to nonionic surfactant may vary, taking the above considerations in mind, and will depend on their nature, but is preferably in the range of from 1:9 to 9:1, more preferably from 1:4 to 4:1, and ideally above 1:1.
  • the cleaning compositions will comprise from 0 to 10% by weight of a water-soluble, synthetic anionic sulphate or sulphonate surfactant salt containing a C 8 -C 22 alkyl group, and from 0.5 to 7% by weight of an ethoxylated alcohol nonionic surfactant having a C 8 -C 22 alkyl group and 2 to 15 ethyleneoxy groups.
  • amphoteric, cationic or zwitterionic surfactants in the compositions according to the invention.
  • Suitable amphoteric surfactants that optionally can be employed are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyl taurate.
  • anionic water-solubilising group for instance sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyl taurate.
  • Suitable cationic surfactants are quaternary ammonium salts having one or two aliphatic groups of from 8 to 18 carbon atoms and two or three small aliphatic (e.g. methyl) groups, for instance cetyltrimethyl ammonium bromide.
  • Suitable zwitterionic surfactants that optionally can be employed are 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 3-(N,N-dimethyl-N-hexadecylammonium) propane-1-sulphonate betaine, 3-(dodecyl methyl sulphonium) propane-1-sulphonate betaine and 3-(cetylmethyl phosphonium) ethane sulphonate betaine.
  • anionic water-solubilising group for instance 3-(N,N-dimethyl-N-hexadecylammonium) propane-1-sulphonate betaine, 3-(dodecyl methyl sulphonium) propane-1-sulphonate betaine and 3-(cetylmethyl phosphonium) ethane sul
  • surfactants are compounds commonly used as surface-active agents given in the well-known textbooks "Surface Active Agents", Volume I by Schwartz and Perry and “Surface Active Agents and Detergents", Volume II by Schwartz, Perry and Berch.
  • the total amount of surfactant compound to be employed will generally be from 0.5 to 20%.
  • the amount is at least 1%, more preferably at least 3%.
  • the maximum amount is usually 15% or less, preferably not more than 10%.
  • the kind of surfactant and its amount is chosen such that it does not form a complex with the polymer which cannot be maintained dissolved or dispersed in the composition.
  • compositions according to the present invention may contain other ingredients which aid in their cleaning performance.
  • the compositions may contain insoluble abrasives such as calcites, silica and other abrasive materials known in the art, or they may contain detergency builders such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates (especially ortho-, pyro- or polyphosphates or mixtures thereof), zeolites and mixtures thereof in an amount of up to 25%. Some of these builders can additionally function as abrasives if present in an amount in excess of their solubility in water. If present, the builder preferably will form at least 0.1% of the composition.
  • Metal ion sequestrants such as ethylenediaminetetraacetates, amino-polyphosphonates (DEQUEST TM ) and phosphates and a wide variety of poly-functional organic acids and salts, can also optionally be employed provided they are compatible with polymer and optional abrasive material.
  • a further optional ingredient for compositions 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.
  • a suds regulating material is soap.
  • Soaps are salts of fatty acids and include alkali metal 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 tri-ethanolamine salts of the mixtures of fatty acids derived from coconut oil and groundnut oil.
  • the amount of soap can form at least 0.005%, preferably 0.1% to 2% by weight of the composition.
  • a further example of a suds regulating material is silicone oil.
  • a further optional ingredient which may be used in compositions according to the invention is an acidic material which helps in removing scale deposits.
  • an acidic material which helps in removing scale deposits. Examples thereof are well known in the art and include phosphoric acid and many di- and polycarboxylic acids.
  • compositions according to the invention can 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 such as active chlorine compounds or hydrogen peroxide, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives (for example 1,2-benzisothiazolin-3-one), perfumes and hydrotropes.
  • various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents such as active chlorine compounds or hydrogen peroxide, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives (for example 1,2-benzisothiazolin-3-one), perfumes and hydrotropes.
  • the hard surface treatment composition can have any suitable pH.
  • compositions are either mildly alkaline (particularly if they are formulated as surface cleaning compositions, in order to enhance the effect of surfactants), neutral or slightly acidic (particularly if they include cationic species or amine groups which become protonated and cationic in an acid environment, in order to assist deposition).
  • the compositions should not be too acidic, in order to avoid damage to acid sensitive surfaces. In particular, it is important to minimise or avoid the presence of sequestering organic acids which are prone to attack surfaces such as enamel.
  • the pH is in the region 3-12, with the ranges 3.5-6.0 and 10-12 being particularly preferred. In any event, the pH is suitably above 3.0 and more preferably above 3.5.
  • polymeric material according to the present invention can, in addition to scale inhibiting effects, give a longer lasting shine, better surface appearance, a smooth feel to treated surfaces.
  • compositions according to the present invention are useful for treating household surfaces in for example kitchens and bathrooms, including walls, floors, toilets, dishwashers, and work surfaces. They are particularly suitable for treating surfaces which are prone to remain in prolonged contact with water such as: shower walls and floors, bath tubs and rims, taps, shower heads, wash basins, sinks and the like.
  • compositions were prepared according to the following formulations (* indicate the nucleation inhibiting polymers):
  • Steel tiles formed of certain surfaces are obtained from Mersey Metals.
  • the tiles were 0.9 mm thickness, 100 x 100 mm square in size, finished to 304 specification with a mirror finish and plastic backed on one side.
  • the tiles are thoroughly cleaned and rinsed using demineralised water. The tiles are then left to dry.
  • a 0.5% by weight aqueous solution of polymer is applied in an even layer to each tile using a K-bar applicator, K-bar number 0010.
  • K-bar applicator K-bar number 0010.
  • 0.5 ml of solution is pipetted across the top edge of the tile next to the K-bar.
  • the driving speed of the K-bar is set to 16.5 cm/s.
  • the tiles are left to dry for up to 24 hours.
  • Dried tiles are then mounted at 10° to the horizontal.
  • Each tile is then rinsed with 200 ml of demineralised water pumped across the tile by a peristaltic pump at a rate of 812 ml/min.
  • the tile is then laid horizontally to dry.
  • Plastic templates in the form of square sheets of acetate film having a square hole in the centre are adhered to each tile.
  • 0.5 ml of Prenton water (27°FH) is added to each tile within the square defined by the plastic template.
  • the drop is left to dry.
  • the step is repeated for 6 x 0.5 ml additions of Prenton water, each of which is left to dry.
  • the treated tiles are then subjected to a cleaning test using a WIRA (Wool Institute Research Association) machine. This apparatus measures the number of cycles required to clean a defined area.
  • the area to be cleaned corresponds to the exposed area defined by the plastic template.
  • the tiles are left to dry and assessed for scale, and tarnish. Scale and tarnish are assessed subjectively and rated on a scale of 1 to 4, 1 corresponding to no or very little removal and
  • Example 2 The method of Example 2 is conducted with the polymeric materials listed in the table below. The tarnish results were assessed and the scores are set out below.
  • Treatment Average score (uncertainty at 95% confidence limit in brackets) Jif (trade mark) cleaned 1.93(7) Surfactant cleaned only 1.7(2) Celquat L200 (trade mark) 2.9(3) JR-30-M (trade mark) 3.6(2) Jaguar C162 (trade mark) 3.4(4) Crotein C (trade mark) 3.6(4)
  • the apparatus described above for measuring nucleation density can be used to test the effect of polymer on nucleation density at a surface, as follows.
  • a 10 mm diameter stainless steel sample (steel type 304) polished to a 0.05 micrometre finish was masked on one half. The other half was treated with a 0.5%wt aqueous solution of polymer.
  • Solution A comprises calcium chloride (obtained from Aldrich 99.99% plus pure) in 0.1 M NaCl (obtained from Fisons, 99.9% plus pure) and solution B comprise NaHCO 3 (obtained from BDH, 99.5% plus pure) in 0.1 M NaCl.
  • concentrations of calcium chloride and sodium bicarbonate are altered to achieve supersaturation of calcium carbonate in a manner known to the person skilled in the art.
  • the pH is regulated to 8.5 using NaOH (obtainable from Fisons, 86% plus pure) or HCl (obtainable from Aldrich, 0.5098 N, ACS grade).
  • Narlex ST15 is not a polymer according to the invention and is included in the table as a comparative example.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Selon l'invention, une matière polymère est déposée sur des surfaces dures de manière à réduire le niveau de nucléation hétérogène d'une surface par formation de sel de calcium. Le tarte est nucléé dans la solution principale, résultant en des sels de calcium plus aisés à éliminer.

Claims (10)

  1. Utilisation d'une substance polymère pour réduire la nucléation hétérogène de sels de calcium et de magnésium au niveau d'une surface dure comprenant le dépôt sur la surface dure d'une substance polymère qui est un polymère naturel modifié avec des espèces contenant de l'azote et dans laquelle la substance polymère possède en outre un poids moléculaire moyen en poids supérieur à 10 000 et des groupes cationiques ou des groupes qui deviennent cationiques au pH d'utilisation.
  2. Utilisation selon la revendication 1, dans laquelle une réduction de la densité de nucléation au niveau de la surface dure d'au moins 10 % est obtenue avec au moins un sel choisi dans le groupe constitué par le carbonate de calcium, le sulfate de calcium, le sulfate de magnésium, le carbonate de magnésium et leurs mélanges, dans la méthode décrite dans ce document en utilisant l'appareil permettant de mesurer la réduction de la densité de nucléation décrit dans ce document et en utilisant un disque de test choisi parmi l'acier inoxydable, la céramique, l'émail, le verre et le Perspex.
  3. Utilisation selon la revendication 1, dans laquelle il est utilisé une substance polymère qui permet de réduire la densité de nucléation d'au moins 10 % à la fois avec le carbonate de calcium et le sulfate de calcium sur toutes les surfaces du groupe constitué de l'acier, du verre, de la céramique et de l'émail.
  4. Utilisation selon les revendications 1 et 2, dans laquelle la substance polymère possède des parties hydrophobes.
  5. Utilisation selon les revendications 1 et 2, dans laquelle la substance polymère comprend des substituants volumineux.
  6. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la substance polymère comprend des groupes de type ammonium quaternaire ou amine tertiaire.
  7. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le polymère naturel est choisi parmi la gomme de guar, la cellulose, la gomme de caroube, l'amidon ou l'amylose.
  8. Utilisation selon la revendication 6, dans laquelle la substance polymère est une gomme de guar cationique ou un polymère polyquaternaire.
  9. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle la substance polymère est déposée à partir d'une composition de nettoyage de surface dure comprenant au moins un tensioactif et d'autres composants de nettoyage de surface dure facultatifs.
  10. Procédé pour empêcher la formation ou l'adhérence du tartre sur des surfaces en métal, en verre ou en plastique dur comprenant l'application sur la surface d'une composition de nettoyage comprenant un tensioactif détersif et une substance polymère selon l'une quelconque des revendications précédentes.
EP00993324A 1999-12-08 2000-11-24 Utilisation de matiere polymere dans le traitement de surfaces dures Revoked EP1235895B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
ES00993324T ES2304360T3 (es) 1999-12-08 2000-11-24 Uso de material polimero en el tratamiento de superficies duras.
EP00993324A EP1235895B1 (fr) 1999-12-08 2000-11-24 Utilisation de matiere polymere dans le traitement de surfaces dures

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP99309884 1999-12-08
EP99309884 1999-12-08
PCT/EP2000/011819 WO2001042415A1 (fr) 1999-12-08 2000-11-24 Utilisation de matiere polymere dans le traitement de surfaces dures
EP00993324A EP1235895B1 (fr) 1999-12-08 2000-11-24 Utilisation de matiere polymere dans le traitement de surfaces dures

Publications (2)

Publication Number Publication Date
EP1235895A1 EP1235895A1 (fr) 2002-09-04
EP1235895B1 true EP1235895B1 (fr) 2008-03-26

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EP00993324A Revoked EP1235895B1 (fr) 1999-12-08 2000-11-24 Utilisation de matiere polymere dans le traitement de surfaces dures

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EP (1) EP1235895B1 (fr)
AR (1) AR033505A1 (fr)
AT (1) ATE390474T1 (fr)
AU (1) AU2837301A (fr)
CA (1) CA2392587C (fr)
DE (1) DE60038458T2 (fr)
ES (1) ES2304360T3 (fr)
HU (1) HUP0203811A3 (fr)
WO (1) WO2001042415A1 (fr)
ZA (1) ZA200203357B (fr)

Cited By (3)

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US8343286B2 (en) 2008-12-02 2013-01-01 Diversey, Inc. Ware washing system containing cationic starch
US8647444B2 (en) 2007-07-05 2014-02-11 Diversey, Inc. Rinse aid
US8876982B2 (en) 2005-05-04 2014-11-04 Diversey, Inc. Warewashing method using a cleaning composition containing low levels of surfactant

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JP2002060786A (ja) * 2000-08-23 2002-02-26 Kao Corp 硬質表面用殺菌防汚剤
DE10055555A1 (de) * 2000-11-09 2002-05-29 Henkel Ecolab Gmbh & Co Ohg Behandlung von Oberflächen zur temporären Verbesserung des Schmutzablöseverhaltens
US6794346B2 (en) * 2001-10-26 2004-09-21 S.C. Johnson & Son, Inc. Hard surface cleaners containing chitosan and furanone
US6849586B2 (en) * 2001-10-26 2005-02-01 S. C. Johnson & Son, Inc. Hard surface cleaners containing chitosan
US7048806B2 (en) 2003-12-16 2006-05-23 The Clorox Company Cleaning substrates having low soil redeposition
GT200600375A (es) * 2005-08-17 2007-03-14 Composición limpiadora ácida que contiene un polímero de hidrofilización
EP1845152A1 (fr) * 2006-04-14 2007-10-17 The Procter and Gamble Company Procédé pour le nettoyage d'une surface dure avec un copolymère zwitterionique
US7741265B2 (en) 2007-08-14 2010-06-22 S.C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
WO2010065481A1 (fr) 2008-12-02 2010-06-10 Diversey, Inc. Nettoyage d'un dispositif ou d'un appareil de cuisson avec une composition comprenant un adjuvant de rinçage intégré
KR20130116256A (ko) * 2010-10-01 2013-10-23 로디아 오퍼레이션스 경질 표면을 위한 세정 조성물
WO2016055264A1 (fr) * 2014-10-09 2016-04-14 Unilever N.V. Composition liquide de nettoyage de surface dure
EP3504312B1 (fr) * 2016-08-25 2020-05-13 Unilever N.V. Composition de traitement de surface dure
EA038572B1 (ru) * 2016-10-12 2021-09-16 ЮНИЛЕВЕР АйПи ХОЛДИНГС Б.В. Композиция для обработки твердых поверхностей

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GB8811953D0 (en) * 1988-05-20 1988-06-22 Unilever Plc General-purpose cleaning compositions
GB9310365D0 (en) * 1993-05-18 1993-06-30 Unilever Plc Hard surface cleaning compositions comprising polymers
GB9315281D0 (en) * 1993-07-23 1993-09-08 Kodak Ltd Method and composition for facilitating the removal of soil contaminants from solid surfaces
CN1196752A (zh) * 1996-05-07 1998-10-21 花王株式会社 硬质表面用液体洗涤剂组合物和硬质表面的清洗方法
DE69723672T2 (de) * 1997-04-30 2004-04-15 The Procter & Gamble Company, Cincinnati Verwendung von Polysacchariden in flüssigen sauren Zusammensetzungen
EP0957156B1 (fr) * 1998-05-15 2005-04-20 The Procter & Gamble Company Composition de nettoyage liquide acide pour surfaces dures

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8876982B2 (en) 2005-05-04 2014-11-04 Diversey, Inc. Warewashing method using a cleaning composition containing low levels of surfactant
US8647444B2 (en) 2007-07-05 2014-02-11 Diversey, Inc. Rinse aid
US8343286B2 (en) 2008-12-02 2013-01-01 Diversey, Inc. Ware washing system containing cationic starch

Also Published As

Publication number Publication date
EP1235895A1 (fr) 2002-09-04
DE60038458T2 (de) 2009-04-02
HUP0203811A2 (hu) 2003-03-28
ATE390474T1 (de) 2008-04-15
HUP0203811A3 (en) 2005-10-28
CA2392587C (fr) 2009-02-03
ES2304360T3 (es) 2008-10-16
WO2001042415A1 (fr) 2001-06-14
AR033505A1 (es) 2003-12-26
DE60038458D1 (de) 2008-05-08
CA2392587A1 (fr) 2001-06-14
AU2837301A (en) 2001-06-18
ZA200203357B (en) 2003-04-29

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