EP0699226B1 - Polymere enthaltende reinigungsmittel für harte oberflächen - Google Patents

Polymere enthaltende reinigungsmittel für harte oberflächen Download PDF

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EP0699226B1
EP0699226B1 EP94915114A EP94915114A EP0699226B1 EP 0699226 B1 EP0699226 B1 EP 0699226B1 EP 94915114 A EP94915114 A EP 94915114A EP 94915114 A EP94915114 A EP 94915114A EP 0699226 B1 EP0699226 B1 EP 0699226B1
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polymer
cleaning
anionic
surfactant
polymers
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EP0699226B2 (de
EP0699226A1 (de
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Martin Sharples
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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

Definitions

  • the present invention relates to general purpose, particularly, hard surface, liquid cleaning compositions comprising surfactants and polymeric components.
  • US 3679592 (1972) discloses alkaline, cleaning and soil preventative compositions which comprise surfactant and 1-10%wt, particularly 4%, of a film forming component of specified structure having a molecular weight in the range 500 to 100,000. In use, the compositions are said to inhibit stain deposition and assist soil removal.
  • GB 1528592 (1978) discloses alkaline, floor cleaning compositions which comprise an organic, polycarboxylic acid co-polymer having a molecular weight in the range 100,000-2,500,000 which is soluble in aqueous solutions having a pH of 8.5 or above. These polymers are readily available in commercial quantities.
  • GB 1534722 (1978) discloses granular hard surface cleaning compositions which comprise surfactant and, as "a soil removal improvement mixture", a polyvinyl alcohol or pyrrolidone and a biopolysaccharide. These polymers have molecular weights ranging from around 5000 to around 360,000 and are available in industrially useful quantities. The compositions form alkaline solutions.
  • US 4252665 (1979) discloses aqueous, alkaline, hard surface cleaning compositions of pH 9-12 which comprise a 'detergency-boosting' acrylic copolymer having a molecular weight substantially in excess of 100,000 in combination with anionic surfactants.
  • surfactant-based cleaning compositions to contain structuring agents to aid in providing appropriate rheological properties to enhance their distribution and adherence of the composition to the hard surface to be cleaned, particularly to provide enhanced cling on sloping surfaces.
  • Known structuring agents include polymers such as polysaccharides, e.g. sodium carboxymethyl cellulose and other chemically modified cellulose materials, xanthan gum and other non-flocculating structuring agents such as Biopolymer PS87 referred to in US Patent No. 4 329 448.
  • Polymers of acrylic acid cross-linked with a poly functional agent, for example CARBOPOL R are also used as structuring agents.
  • the amount of such structuring agents can be as little as 0.001% but is more typically at least 0.01% by weight of the composition.
  • a further function of such structuring agents is to suspend particulate components, such as abrasives.
  • At least partially esterified resins such as an at least partially esterified adduct of rosin and an unsaturated dicarboxylic acid or anhydride, or an at least partially esterified derivatives of copolymerisation products of mono-unsaturated aliphatic, cycloaliphatic or aromatic monomers having no carboxy groups and unsaturated dicarboxylic acids or anhydrides thereof as additives.
  • the purpose of such materials is to modify the wetting properties of the composition so as to produce a 'streak-free' finish after drying.
  • Suitable copolymers of the latter type are copolymers of ethylene, styrene and vinyl-methylether with maleic acid, fumaric acid, itaconic acid, citraconic acid and the like and the anhydrides thereof including the styrene/maleic anhydride copolymers.
  • EP 0467472 A2 discloses that soil release promoting polymers such as, but not limited to, the cationic poly[beta(methyl diethyl-ammonium) ethyl-methacrylate] are also effective in combination with anionic and cationic surfactant .
  • 'said adsorbed polymer forms a residual anti-soiling hydrophilic layer of said soil release promoting polymer on said surface, whereby removal of soils subsequently deposited thereupon requires less work than in the absence of said residual layer'.
  • the molecular weight range of the polymers falls into the range 4,000-100,000 although the use of polymers having a molecular weight above 50,000 is discouraged for solubility reasons (see EP 467472, page 3 paragraph 3).
  • EP 0379256 discloses similar compositions to the above-mentioned document, having up to 2%wt of an optional quaternised, anti-static, polymer of molecular weight in the range of 2,000 - 500,000, and being characterised by an acidic pH of 2-4 and a 2-4%wt of a nonionic surfactant system. Specific examples relate to compositions having a pH of 2.5 and comprising 2.2%wt of a mixed nonionic system and 0.07% of the specified cationic polymer. The modified polymer is again said to function as a soil release agent.
  • US 4678596 relates to a rinse aid formulation for hand dishwash and machine dishwash of pH 7.5-10, which comprises 5-60% nonionic surfactant (examples are 15%), and preferably 2%wt of anionic poly(meth)acrylic acid polymer of molecular weight 1,000-50,000.
  • Compositions having a pH of 6.5 comprising relatively high levels of polymer are said to be unstable.
  • US 4657690 relates to a washing and foaming composition for hair and skin in the acid/neutral pH range (4.5-7.7) which comprises nonionic surfactant (typically at around 5%) and poly(meth)acrylic acid to improve the primary detergency of the surfactant wherein the weight ratio of the polymer to the surfactant is no greater than 0.2:1.
  • nonionic surfactant typically at around 5%
  • poly(meth)acrylic acid to improve the primary detergency of the surfactant wherein the weight ratio of the polymer to the surfactant is no greater than 0.2:1.
  • liquid hard-surface cleaning composition of pH 3-7 comprising:
  • the cleaning benefit of the water-soluble polymer arises from a phase separation of the nonionic surfactant causing penetration into and/or deposition onto soil, resulting in a higher effective surfactant concentration, than is found in compositions which are free of polymer.
  • An alternative explanation is that deposition of surfactant at the soil surface may be enhanced by the formation and deposition of a polymer surfactant complex.
  • the water soluble polymer of the above-mentioned size range is an essential component of the compositions according to the present invention.
  • the preferred polymers in embodiments of the present invention are those which are readily available in the marketplace. These are polymers of acrylic or methacrylic acid or maleic anhydride, or a co-polymer of one or more of the same either together or with other monomers.
  • Particularly suitable polymers include polyacrylic acid, polymaleic anhydride and copolymers of either of the aforementioned with ethylene, styrene and methyl vinyl ether.
  • the most preferred polymers are maleic anhydride copolymers, preferably those formed with styrene, acrylic acid, methyl vinyl ether and ethylene.
  • the molecular weight of the polymer is at least, 5000, more preferably at least 50,000 and most preferably in excess of 100,000.
  • the surfactant based cleaning compositions comprise at least 0.01wt% polymer, on product.
  • the level of polymer is 0.05-5.0wt% at which level the anti-resoiling benefits become particularly significant. More preferably 0.2-2.0wt% of polymer is present.
  • higher levels of polymer do not give significant further advantage with common dilution factors, while increasing the cost of compositions. It is believed that high levels of polymer increase the viscosity of the product and hinder product wetting and penetration of the soil.
  • the initial polymer level can be as high as 5%wt.
  • anionic polymers are those which carry a negative charge or similar polymers in protonated form. Mixtures of polymers can be employed.
  • the molecular weight of the polymer is below 1 000 000 Dalton. As the molecular weight increases the cleaning benefit of the polymer was reduced.
  • compositions according to the present invention comprise at least one nonionic surfactant.
  • composition according to the invention comprise detergent actives which can be chosen from nonionic detergent actives. We have determined that an detrimental effect occurs if the anionic polymers are used together with anionic surfactant only or with mixtures of anionic and nonionic surfactant which largely comprise anionic surfactant.
  • Suitable nonionic detergent active compounds 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 condensates containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 11,000; tertiary amine oxides of structure R 3 N0, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxy-ethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides of
  • the amount of nonionic detergent active to be employed in the composition of the invention will generally be from 1 to 30%wt, preferably from 10 to 20%wt, and most preferably from 12 to 20%wt. Levels of around 15% active are particularly preferred as little increase in neat-use cleaning performance is found at higher levels, although such higher levels can be employed in products intended to be considerably diluted prior to use.
  • anionic surfactant can be present in relatively small proportions.
  • Suitable anionic detergent active compounds are water-soluble salts of organic sulphuric reaction products having in the molecular structure an alkyl radical containing from 8 to 22 carbon atoms, and a radical chosen from sulphonic acid or sulphur acid ester radicals and mixtures thereof.
  • anionic detergents are sodium and potassium alcohol sulphates, especially those obtained by sulphating the higher alcohols produced by reducing the glycerides of tallow or coconut oil; sodium and potassium alkyl benzene sulphonates such as those in which the alkyl group contains from 9 to 15 carbon atoms; sodium and potassium secondary alkanesulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulphates; sodium and potassium salts of sulphuric acid esters of the reaction product of one mole of a higher fatty alcohol and from 1 to 6 moles of ethylene oxide; sodium and potassium salts of alkyl phenol ethylene oxide ether sulphate with from 1 to 8 units of ethylene oxide molecule and in which the alkyl radicals contain from 4 to 14 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutral
  • the preferred water-soluble synthetic anionic detergent active compounds are the ammonium and substituted ammonium (such as mono, di and triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of higher alkyl benzene sulphonates and mixtures with olefinsulphonates and higher alkyl sulphates, and the higher fatty acid monoglyceride sulphates.
  • ammonium and substituted ammonium such as mono, di and triethanolamine
  • alkali metal such as sodium and potassium
  • alkaline earth metal such as calcium and magnesium
  • the most preferred anionic detergent active compounds are higher alkyl aromatic sulphonates such as higher alkyl benzene sulphonates 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 higher alkyl benzene sulphonates or of higher-alkyl toluene, xylene or phenol sulphonates, alkyl naphthalene sulphonates, ammonium diamyl naphthalene sulphonate, and sodium dinonyl naphthalene sulphonate.
  • higher alkyl aromatic sulphonates such as higher alkyl benzene sulphonates 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 higher alkyl benzene sulphonates or of higher-alkyl toluene, xylene or
  • the amount of synthetic anionic detergent active to be employed in the detergent composition of this invention will generally be from 0.5 to 50%wt (on total active), preferably less than 33%wt (on total active).
  • the level of anionic surfactant should preferably not exceed 5%wt on product.
  • amphoteric, cationic or zwitterionic detergent actives in the compositions according to the invention.
  • Suitable amphoteric detergent-active compounds 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 radical substituted by an anionic water-solubilising group, for instance sodium 3-dodecylamino-propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyltaurate.
  • Suitable cationic detergent-active compounds are quaternary ammonium salts having an aliphatic radical of from 8 to 18 carbon atoms, for instance cetyltrimethyl ammonium bromide.
  • Suitable zwitterionic detergent-active compounds that optionally can be employed 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-hexadecylammoniumlpropane-1-sulphonate betaine, 3-(dodecylmethyl sulphonium) propane-1-sulphonate betaine and 3-(cetylmethylphosphonium) ethane sulphonate betaine.
  • anionic water-solubilising group for instance 3-(N,N-dimethyl-N-hexadecylammoniumlpropane-1-sulphonate betaine, 3-(dodecylmethyl sulphonium) propane-1-sulphonate betaine and 3-(cetylmethylphosphonium) ethane s
  • detergent-active compounds 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 detergent active compound to be employed in the detergent composition of the invention will generally be from 1.5 to 30%, preferably from 2 to 20% by weight, most preferably from 10-20wt%.
  • composition according to the invention can contain other ingredients which aid in their cleaning performance.
  • the composition can contain detergent builders other than the special water-soluble salts, as defined herein, such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates especially polyphosphates, mixtures of ortho-and pyrophosphate, zeolites and mixtures thereof.
  • Such builders can additionally function as abrasives if present in an amount in excess of their solubility in water as explained herein.
  • the builder, other than the special water-soluble salts when employed preferably will form from 0.1 to 25% by weight of the composition.
  • Metal ion sequestrants such as ethylenediaminetetraacetates, amino-polyphosphonates (DEQUEST R ) and phosphates and a wide variety of other polyfunctional organic acids and salts, can also optionally be employed.
  • a further optional ingredient for compositions according to the invention is a suds regulating material, which can be employed in compositions according to the invention 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 soaps such as the sodium, potassium, ammonium and alkanol ammonium salts of higher 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 coconut oil and ground nut oil.
  • the amount of soap can form at least 0.005%, preferably 0.5% to 2% by weight of the composition.
  • a further example of a suds regulating material is an organic solvent, hydrophobic silica and a silicone oil or hydrocarbons.
  • compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, solvents, fungicides, insect repellents, detergent hydrotropes perfumes and opacifiers.
  • various other optional ingredients such as pH regulants, colourants, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, bactericides, preservatives, solvents, fungicides, insect repellents, detergent hydrotropes perfumes and opacifiers.
  • compositions of the present invention are essentially free of abrasive particles.
  • abrasive reduces the cleaning benefit due to the polymer although abrasive would in itself provide a separate cleaning benefit. It is believed that the abrasive, surfactant and polymer form a complex which reduces the effective concentration of the surfactant at the surface being cleaned.
  • the pH of the compositions according to the present invention is acidic or neutral. We have determined that improved cleaning and/or anti-resoiling benefit is obtained at these pH's.
  • the preferred pH of the products is in the range 3-6.
  • a pH of 4-6 is particularly preferred so as to provide a balance between the hazards of acid compositions and the advantages of acids for removing limescale.
  • compositions according to the present invention are mobile aqueous liquids, having a pH of 3-6 which comprise:
  • Examples 1-8 use materials as mentioned below: Sokolan series (TM) ex. BASF Gantrez series (TM) ex. GAF Scripset 520 (TM) ex Monsanto EMA 31 ex Monsanto SCMC (Courlose A600) ex Courtaulds 6047 polyacrylamides ex. Allied Colloids FRS 3966 ex. Allied Colloids Jaguar C162 ex Meyhall Polyethylene Oxide (WSRN 80) ex Union Carbide Polyvinyl Pyrrolidone ex PolySciences
  • the polyvinyl pyrrolidone had a molecular weight of circa. 386000 Dalton.
  • 0.25mg/cm 2 (based on non-volatiles) of soil were deposited on an 'A4' sized area of 'DECAMEL' (RTM ex Formica) test surface by spraying.
  • the soil comprised 1% glycerol tripalmitate, 0.5% glycerol trioleate, 0.5% kaolin, 0.2% liquid paraffin, 0.1% palmitic acid, 0.02% carbon black in methylated spirits.
  • the soil was allowed to age for 24 hours at room temperature prior to cleaning.
  • Formulations comprised nonionic surfactant and water with and without polymer.
  • the surfactant employed was Imbentin 91-35 OFA (TM) (C9-C11 alkyl, 3-5 EO alkyl ethoxylate ex. KOLB).
  • the polymers illustrative of the present invention were a polyacrylic acid (ex BDH) which had an average molecular weight of 230,000 Daltons.
  • the cationic polymer used in the comparative examples was Polymer JR-400 (TM: ex. Union Carbide) and had an average molecular weight of 400,000 Daltons.
  • Table 1 The formulations are given in Table 1 below, together the effort required in the cleaning operation.
  • Results given are geometric means of eight replicate experiments. In order to remove day to day variability, arising from differences in soil level data is normalised such that the effort required to clean a DECAMEL tile with the same polymer-free composition is constant.
  • compositions according to the present invention show an improved cleaning performance over the comparative example 1a, where no polymer was present. This improvement is statistically significant at the 95% confidence level.
  • Results given under 'normal(4)' are results obtained by subsequently cleaning the test surfaces used in examples 1a-e with the composition used in example 1a (i.e. surfactant alone). This indicates that the benefit of the present invention persisted when the test surfaces were cleaned with a conventional surfactant-only composition.
  • Example 1 was repeated using the formulations given in Table 2 below: except that the polyacrylacid used was VERSICOL E11 (RTM) (ex. Allied Colloids: mol wt 250kD). Effort to clean the DECAMEL (RTM) tiles is expressed in terms of the logarithm (base 10) of the effort required. Examples were repeated both with and without polymer and at differing concentrations of surfactant. The values given are the means of four replicates.
  • 'Same(2)' values were obtained by re-cleaning the tiles originally cleaned with the polymer-containing composition, to obtain the results given at 'Initial(1)' using the same composition in the same manner as the tiles had initially been cleaned.
  • 'Normal(2)' values were obtained by cleaning the re-soiled tiles from 'Normal(1)' with a polymer free composition having the same surfactant level.
  • Normal (3-5) values were obtained by cleaning the tiles originally cleaned by a polymer-containing composition (to obtain the 'Same(2)' results) with a polymer-free composition. In all the recleanings in the Normal(3-5) series the same level of surfactant (7%wt: IMBENTIN) was used.
  • compositions comprising the low levels of surfactant and polymer clean at least as well as the compositions containing higher levels of these components: compare 2d with 2f in which four times the levels of surfactant and polymer are present yet the same effort was required to clean the tile. Compositions which contain no polymer do not clean when only low levels of surfactant are present. It was also determined that compositions which contain no polymer show no reduction in effort required on repeated use.
  • Examples 2h-2l compare the effort required using very dilute solutions of the products listed in Table 2c.
  • the compositions are diluted to typical floor-cleaning dilutions as recommended by the manufacturers (approximately 3g/l).
  • the formulation of the embodiment of the invention is: 28% IMBENTIN, 2% polyacrylic acid (250kD: VERSICOL E11 (RTM), ex Allied Colloids).
  • the formulation of the comparative example using nonionic alone omitted the polymer.
  • Results for percentage soil removal on a hydrophobic surface determined by a standard colourimetric method, after 40 cleaning strokes, were obtained using an in-line linear scrubber of the SHEEN (RTM) type using an applied pressure of 80g/cm2.
  • the surface was DECAMEL (RTM) and pre-soiled with 0.061mg/cm2 (based on non-volatiles) of soil. Cleaning was performed with a cellulosic sponge pre-impregnated with the appropriate cleaning solution.
  • Results for percentage soil removal on a hydrophilic surface were determined using the same soil applied to ceramic floor tiles, under identical conditions but with a single cleaning stroke.
  • Example 1 was repeated using simplified formulations consisting of anionic surfactant only in water with and without anionic or cationic polymer.
  • the surfactant employed was a magnesium salt of PAS.
  • the anionic polymer was polyacrylic acid as used in example 1.
  • the cationic polymer was Polymer JR as used in example 1.
  • Table 4 The formulations are given in Table 4 below, together the effort required in the cleaning operation as mentioned in example 1. Figures given are geometric means of eight replicate experiments, normalised to represent the data as if compositions free of polymer always require the same cleaning effort.
  • Results given under 'Normal(4)' are results obtained by subsequently cleaning the test surfaces used in examples 3a-e with the composition used in example 3a, i.e. cleaning with surfactant only (an essentially conventional composition) in the absence of polymer. This indicates that the negative benefit of anionic polymers persisted when the test surfaces were cleaned with a conventional surfactant-only composition. These results also show that cationic polymers exhibit a secondary cleaning benefit which is not seen with anionic polymers in the presence of anionic surfactant.
  • Results were normalised such that the initial cleaning effort required with the surfactant alone was 100%.
  • the recleaning benefit was assessed by cleaning the surfaces with a 7.5wt% aqueous solution of nonionic surfactant alone and measuring the effort required: results again being normalised assuming 100% cleaning effort for surfactant alone.
  • nonionic polymers as mentioned in GB 1534722 such as the coating agents PO (at 49,29) and PVP (at 43,37), show particularly poor recleaning benefits although the primary cleaning performance is good.
  • the cationic polymers show some benefits both in primary and secondary cleaning, although the trend indicates that the two factors have an inverse relationship, that is, better cleaning in one situation is generally associated with worse performance in the other: compare polyacrylamide at (82,16) and polyacrylamide at (42,26).
  • FIG 1 there is shown a graph of the effect of polymer concentration (230kD, ex BDH) on cleaning effort and anti-resoiling benefit. All compositions were at the natural pH of 4, and comprised surfactant (Imbentin 91-35 OFA: C9-C11 alkyl, 3-5 EO alkyl ethoxylate) at a level of 10%wt. The cleaning and anti-resoiling benefits were assessed as in Example 4.
  • surfactant Imbentin 91-35 OFA: C9-C11 alkyl, 3-5 EO alkyl ethoxylate
  • Table 6 shows the effect of pH for compositions of the present invention comprising 0.5% of a polyacrylic acid polymer (230kD, ex BDH) and comparative compositions which do not contain polymer. All compositions comprised surfactant (Imbentin 91-35 OFA: C9-C11 alkyl, 3-5 EO alkyl ethoxylate) at a level of 10%wt. pH was modified by the presence of NaOH. The cleaning and anti-resoiling benefits were assessed as in Example 4. Cleaning effort is expressed as the logarithm (base 10) of the effort required.
  • surfactant Imbentin 91-35 OFA: C9-C11 alkyl, 3-5 EO alkyl ethoxylate

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Claims (7)

  1. Flüssige Zusammensetzung zur Reinigung harter Oberflächen mit einem pH-Wert von 3-7, die die folgenden Bestandteile umfaßt:
    a) 1-30 Gew.-% nichtionisches grenzflächenaktives Mittel,
    b) 0,005-3 Gew.-% eines wasserlöslichen, anionischen Polymers mit einem mittleren Molekulargewicht von weniger als 1.000.000, wobei das Polymer keine quaternären Stickstoffgruppen aufweist und wobei das Verhältnis Polymer/nichtionische Verbindung 0,1:1 oder weniger beträgt.
  2. Zusammensetzung nach Anspruch 1, die 0,2-2,0 Gew.-% anionisches Polymer umfaßt.
  3. Zusammensetzung nach Anspruch 1, wobei das anionische Polymer unter Polymeren von Acryl- oder Methacrylsäure oder Maleinsäureanhydrid, Copolymeren eines oder mehrerer dieser Bestandteile zusammen mit einem anderen der obigen genannten oder mit anderen Monomeren und Gemischen hiervon ausgewählt ist.
  4. Zusammensetzung nach Anspruch 3, wobei das Polymer unter Polyacrylsäure, Polymaleinsäureanhydrid und Copolymeren eines der obengenannten Verbindungen mit Ethylen, Styrol und Methylvinylether ausgewählt ist.
  5. Zusammensetzung nach Anspruch 1, wobei das Molekulargewicht des Polymers über 100.000 beträgt.
  6. Zusammensetzung nach Anspruch 1, die nicht mehr als 33 Gew.-% anionisches Reinigungsmittel, bezogen auf alle Reinigungsmittelaktivstoffe, umfaßt.
  7. Flüssige Reinigungszusammensetzung nach Anspruch 1 mit einem pH-Wert von 3-6, die die folgenden Bestandteile umfaßt:
    a) 10-20 Gew.-% eines nichtionischen grenzflächenaktivenalkoxylierten Alkohols,
    b) weniger als 3 Gew.-% anionische grenzflächenaktive Mittel,
    c) 0,2-2 Gew.-% eines wasserlöslichen anionischen Polymers
    mit einem mittleren Molekulargewicht von weniger als 1.000.000, wobei das Polymer aus einem Homo- oder Heteropolymer mindestens eines Bestandteils aus Acrylsäure, Methacrylsäure oder Maleinsäureanhydrid mit mindestens einem Bestandteil aus Acrylsäure, Methacrylsäure, Maleinsäureanhydrid, Ethylen, Styrol und Methylvinylether besteht und im wesentlichen keine quaternären Stickstoffgruppen aufweist.
EP94915114A 1993-05-18 1994-04-26 Polymere enthaltende reinigungsmittel für harte oberflächen Expired - Lifetime EP0699226B2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB939310365A GB9310365D0 (en) 1993-05-18 1993-05-18 Hard surface cleaning compositions comprising polymers
GB9310365 1993-05-18
PCT/EP1994/001290 WO1994026858A1 (en) 1993-05-18 1994-04-26 Hard surface cleaning compositions comprising polymers

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EP0699226A1 EP0699226A1 (de) 1996-03-06
EP0699226B1 true EP0699226B1 (de) 1997-02-26
EP0699226B2 EP0699226B2 (de) 2001-11-07

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EP94915114A Expired - Lifetime EP0699226B2 (de) 1993-05-18 1994-04-26 Polymere enthaltende reinigungsmittel für harte oberflächen

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EP (1) EP0699226B2 (de)
JP (1) JP2750001B2 (de)
KR (1) KR100221768B1 (de)
AU (1) AU698794B2 (de)
BR (1) BR9406406A (de)
CA (1) CA2161324C (de)
CZ (1) CZ302495A3 (de)
DE (1) DE69401815T3 (de)
ES (1) ES2098939T3 (de)
GB (1) GB9310365D0 (de)
HU (1) HU217990B (de)
IN (1) IN181393B (de)
PL (1) PL178776B1 (de)
SK (1) SK280781B6 (de)
TW (1) TW442567B (de)
WO (1) WO1994026858A1 (de)
ZA (1) ZA943260B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2981601B1 (de) 2013-04-03 2016-08-17 Unilever N.V. Flüssigreinigungszusammensetzung

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5650473A (en) * 1994-07-22 1997-07-22 National Starch And Chemical Investment Holding Corporation Methods for making styrene copolymers and uses thereof
US5990066A (en) * 1995-12-29 1999-11-23 The Procter & Gamble Company Liquid hard surface cleaning compositions based on carboxylate-containing polymer and divalent counterion, and processes of using same
US5962398A (en) * 1997-01-14 1999-10-05 Lever Brothers Company Isotropic liquids incorporating anionic polymers which are not hydrophobically modified
GB9704989D0 (en) * 1997-03-11 1997-04-30 Unilever Plc Improvements relating to hard-surface cleaning compositions
DE69722768T2 (de) * 1997-04-30 2004-05-19 The Procter & Gamble Company, Cincinnati Saure Zusammensetzungen zum Entfernen von Kalkstein
EP0892039A1 (de) * 1997-07-18 1999-01-20 The Procter & Gamble Company Flüssige Reinigungszusammensetzungen
DE60038458T2 (de) * 1999-12-08 2009-04-02 Unilever N.V. Verwendung von polymerem material zur behandlung harter oberflächen
DE10055555A1 (de) * 2000-11-09 2002-05-29 Henkel Ecolab Gmbh & Co Ohg Behandlung von Oberflächen zur temporären Verbesserung des Schmutzablöseverhaltens
KR20040039615A (ko) * 2002-11-04 2004-05-12 애경산업(주) 기포력과 저온안정성이 우수한 액체 세제 조성물
ES2360016T5 (es) 2008-06-24 2015-05-05 Cognis Ip Management Gmbh Detergentes que contienen copolímeros de injerto
EP2154111A1 (de) 2008-07-10 2010-02-17 Cognis IP Management GmbH Wasserlösliche Silikate und deren Verwendung
KR101723248B1 (ko) 2008-12-02 2017-04-04 디버세이, 인크 양이온성 전분을 포함하는 식기 세척 시스템
AU2009322572B2 (en) 2008-12-02 2014-07-17 Diversey, Inc. Cleaning of a cooking device or appliance with a composition comprising a built-in rinse aid
EP2228426A1 (de) * 2009-03-13 2010-09-15 Rohm and Haas Company Wassersteinreduzierendes Additiv für automatische Geschirrspülsysteme
KR20130116256A (ko) * 2010-10-01 2013-10-23 로디아 오퍼레이션스 경질 표면을 위한 세정 조성물
WO2014040869A1 (en) * 2012-09-12 2014-03-20 Unilever N.V. Hard surface treatment composition
DE102016202525A1 (de) * 2016-02-18 2017-08-24 Pallmann GmbH Vorbehandlungsmittel für Holz
AU2022249170A1 (en) 2021-04-01 2023-10-12 Sterilex, Llc Quat-free powdered disinfectant/sanitizer

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU84753A1 (fr) * 1983-04-15 1984-11-28 Oreal Composition lavante et moussante a base d'agents tensio-actifs non ioniques et de polymeres anioniques
DE3320727A1 (de) † 1983-06-09 1984-12-13 Henkel KGaA, 4000 Düsseldorf Verwendung von fettsaeurecyanamiden als tenside zum reinigen von harten oberflaechen
US4678596A (en) * 1986-05-01 1987-07-07 Rohm And Haas Company Rinse aid formulation
GB8721936D0 (en) † 1987-09-18 1987-10-28 Rohm & Haas Composition
US5205960A (en) † 1987-12-09 1993-04-27 S. C. Johnson & Son, Inc. Method of making clear, stable prespotter laundry detergent
US4797223A (en) † 1988-01-11 1989-01-10 Rohm And Haas Company Water soluble polymers for detergent compositions
US5008030A (en) † 1989-01-17 1991-04-16 Colgate-Palmolive Co. Acidic disinfectant all-purpose liquid cleaning composition
JP2602563B2 (ja) † 1989-12-15 1997-04-23 花王株式会社 液体酸素系漂白剤組成物
CA2047085A1 (en) † 1990-07-16 1992-01-17 Karen L. Wisniewski Hard surface liquid cleaning composition with soil release polymer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2981601B1 (de) 2013-04-03 2016-08-17 Unilever N.V. Flüssigreinigungszusammensetzung

Also Published As

Publication number Publication date
GB9310365D0 (en) 1993-06-30
HUT73043A (en) 1996-06-28
WO1994026858A1 (en) 1994-11-24
PL178776B1 (pl) 2000-06-30
EP0699226B2 (de) 2001-11-07
SK280781B6 (sk) 2000-07-11
CA2161324C (en) 2005-01-18
AU6648394A (en) 1994-12-12
JP2750001B2 (ja) 1998-05-13
PL311696A1 (en) 1996-03-04
SK140195A3 (en) 1996-03-06
HU9501991D0 (en) 1995-09-28
EP0699226A1 (de) 1996-03-06
BR9406406A (pt) 1995-12-19
DE69401815D1 (de) 1997-04-03
CA2161324A1 (en) 1994-11-24
ZA943260B (en) 1995-11-13
JPH08510276A (ja) 1996-10-29
AU698794B2 (en) 1998-11-05
ES2098939T3 (es) 1997-05-01
IN181393B (de) 1998-06-06
HU217990B (hu) 2000-05-28
TW442567B (en) 2001-06-23
KR100221768B1 (ko) 1999-09-15
CZ302495A3 (en) 1996-03-13
DE69401815T3 (de) 2002-04-04
DE69401815T2 (de) 1997-06-12

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