EP0971997A1 - Hard-surface cleaning compositions - Google Patents
Hard-surface cleaning compositionsInfo
- Publication number
- EP0971997A1 EP0971997A1 EP98912446A EP98912446A EP0971997A1 EP 0971997 A1 EP0971997 A1 EP 0971997A1 EP 98912446 A EP98912446 A EP 98912446A EP 98912446 A EP98912446 A EP 98912446A EP 0971997 A1 EP0971997 A1 EP 0971997A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- alkyl
- surfactant
- cleaning
- compositions
- 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.)
- Granted
Links
Classifications
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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
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
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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
- C11D1/835—Mixtures of non-ionic with cationic compounds
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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
- C11D3/16—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
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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
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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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
Definitions
- the present invention relates to general purpose, hard surface, liquid cleaning compositions comprising nonionic surfactants and polymeric components.
- compositions for cleaning hard surfaces generally comprise one or more nonionic surfactants as cleaning agents involved in the removal of soil from the surface.
- Nonionic surfactants have far better fatty soil detergency than charged surfactants and are typically used in general purpose cleaning compositions for hard surfaces such as kitchen worktops, bathroom fittings, floors and the like.
- nonionic surfactants typically comprise alkoxylated alcohols 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; alternatives include 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 .
- WO 94/26858 discloses how cleaning compositions which deposit a protective film of polymer may be prepared at acid pH's. As is noted in WO 94/26858, the benefit of these polymers was lost as the pH of the prior products was increased. Furthermore, one recognised difficulty with acid products is that they have the potential to damage certain surfaces, particularly enamels such as those used on baths. It is also preferred that cleaning compositions should be formulated at high pH so as to give particularly good fatty soil detergency. It is therefore desirable to be able to formulate products across the entire pH range 3-11 while maintaining the soil release and low effort cleaning benefits outlined in the above mentioned case.
- a hard surface cleaning composition of pH 3-12 comprising:
- a water soluble, anionic polymer having an average molecular weight of less than 1000000, said polymer being free of quaternary nitrogen groups, wherein, the ratio of polymer:nonionic is 0.1:1 or less, and,
- a further aspect of the present invention relates to a method for cleaning hard surfaces which comprises the step of treating the surface with a cleaning composition of pH 3-12 comprising:
- the deposition of the complex on the surface has two results. Firstly the concentration of the surfactant at the surface is increased, resulting in improved cleaning in the initial cleaning cycle and a reduction in the so-called primary cleaning effort. It is also believed that the complex, or at least some part of it, remains on the surface after cleaning and prevents or reduces the re- attachment of soil to the surface thereby making the surface easier to clean in second and subsequent cleaning cycles, i.e. it reduces the 'secondary' cleaning effort.
- compositions according to the invention can also provide an antimicrobial effect during primary cleaning where the cationic is antimicrobial.
- Using compositions according to the invention it is possible to achieve a log 5 reduction in populations of bacteria.
- compositions according to the invention which contain antimicrobial cationic surfactants show longer lasting hygiene on surfaces which have been treated with the compositions and can maintain the antimicrobial effect even after the surfaces have been rinsed. This is believed to be due in part to the retention of antimicrobial components of the formulation at the surface and may be due in part to the formulation preventing re-adhesion of microbes on the surface.
- a third aspect of the present invention relates to the use, in a surface cleaning composition comprising nonionic surfactant and an antimicrobial cationic surfactant, of a water soluble, anionic polymer having an average molecular weight of less than 1000000, said polymer being free of quaternary nitrogen groups, to prolong the antimicrobial effectiveness of the antimicrobial cationic surfactant on said surface.
- compositions of the invention can comprise other benefit components which become deposited at the surface during a cleaning operation performed with such a composition.
- the water soluble polymer is an essential component of the compositions according to the present invention.
- the polymers according to the invention are water soluble polymers having an average molecular weight of less than 1000000, and being free of quaternary nitrogen groups. Typically, these polymers are polymers bearing carboxylate functional groups although the use of other anionic polymers is not excluded. In the context of the present invention, anionic polymers are those which carry a negative charge or similar polymers in protonated form. Mixtures of polymers can be employed.
- 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 co-polymers, 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.
- VERSICOL E-ll [RTM] (ex. Allied Colloids) which is a polyacrylic acid, has been found to be a suitable polymer for use in compositions according to the invention.
- the surfactant based cleaning compositions comprise at least 0.01wt% polymer, on product.
- the positive benefit of the presence of polymer as regards the improvement in cleaning properties can be identified even when very low levels of polymer and surfactant are present. This property of a low concentration threshold is particularly advantageous in applications of the invention where considerable dilution is expected, such as in floor cleaning.
- 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 cleaning advantages 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.
- the molecular weight of the polymer is preferably below 1 000 000 Dalton. It is believed that as the molecular weight increases the cleaning benefit of the polymer is reduced.
- compositions according to the present invention comprise at least one nonionic surfactant.
- the composition according to the invention comprise detergent actives which can be chosen from commercially available nonionic detergent actives.
- 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. Alkoxylated alkanols are particularly preferred.
- 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.
- the compounds will be alkoxylated alcohols having C8-C22 alkyl chains and 1-20 molar equivalents of ethylene oxide and/or propylene oxide residues attached thereto.
- Particular examples include the condensation product of aliphatic alcohols having from 8 to 18 carbon atoms in either straight or branched chain configuration with 2-15 moles of ethylene oxide.
- Examples of such materials include 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 .
- the preferred nonionic surfactants are the condensation products of 9-15 carbon alcohols with 3-10 moles of ethylene oxide.
- DOBANOL [RTM] series ethoxylated alcohol nonionic surfactants (ex. Shell) are suitable.
- Preferred materials include DOBANOL 91-5 [TM] (C9-C11 alkyl, 5 EO alkyl ethoxylate ex. Shell) and DOBANOL 91-8 [TM] (C9-C11 alkyl, 8 EO alkyl ethoxylate ex. Shell).
- Nonionic surfactant materials which are envisaged include 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 structure R 3 P0, where one group R is an alkyl group of from 10 to 18 carbon atoms, and the others are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyldodecylphosphine oxide; and dialkyl sulphoxides of structure R j SO where the group R is an alkyl group of from 10 to 18 carbon
- 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 3 to 15%wt. Levels of above 15% active show little increase in neat-use cleaning performance, although such higher levels can be employed in products intended to be considerably diluted prior to use. Typical compositions will comprise 5-10%wt nonionic active on product. Anionic surfactant can be present in relatively small proportions, however it is preferable that anionic surfactant is absent from composition. As described in further detail below small amounts of anionic detergents may be present in the form of soaps as part of an antifoam system. It is preferred that the compositions of the invention comprise less than 2%wt, preferably less than 1% of anionic surfactant.
- the cationic surfactants are materials of the general formula R 1 R 2 R 3 R 4 N + X " , wherein all of the radicals are hydrocarbons with or without hydroxy substitution, at least one of the radicals R1-R4 is a C6-C22 alkyl, alkaryl or hydroxyalkyl , at least one of the radicals R1-R4 is a C1-C4 alkyl or hydroxy alkyl and X is a onovalent anion equivalent.
- the cationic surfactants are preferably, quaternary nitrogen compounds of the general formula R.R 2 R 3 R 4 N + X ⁇ , where Rl and R2 are the same or different C1-C4 alkyl or hydroxy alkyl, R3 is a C6-C22 alkyl, alkaryl or hydroxyalkyl, R4 is a C1-C22 alkyl, alkaryl or hydroxyalkyl and X is a monovalent anion equivalent .
- X is a halogen, most preferably chloride or bromide .
- Rl and R2 are methyl.
- R3 is preferably C8-C18 alkyl, more preferably C10-
- the cationic surfactants used can have three 'short chain' radicals such as methyl and one fatty-soluble 'long chain' radical or two 'short' chains and two fatty-soluble 'long chains', wherein the ' long chains ' can be either linear or branched hydrocarbons or contain aromatic rings.
- compositions according to the invention which contain antimicrobial cationic surfactants show longer lasting hygiene on surfaces which have been treated with the compositions.
- Particularly suitable cationic detergent-active compounds include cetyltrimethyl ammonium bromide (CTAB) , hardened di- tallow di-methyl ammonium chloride (available in the marketplace as BARDAC 2250), benzalkonium chloride and mixtures thereof .
- CTAB cetyltrimethyl ammonium bromide
- BARDAC 2250 hardened di- tallow di-methyl ammonium chloride
- benzalkonium chloride and mixtures thereof .
- the cationic surfactants which comprise one aryl substituent are especially preferred as they are believed to give particularly good antimicrobial effects.
- Typical levels of cationic surfactant will lie in the range of 0.05-3%wt on product. Preferred levels of cationic surfactant are around l-3%wt.
- 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 5-20wt%.
- Solvents may be present in the compositions of the invention.
- compositions of the present invention comprise not more than 2%wt of solvents of the general formula :
- R t and R 2 are independently C2-6 alkyl or H, but not both hydrogen, m and n are independently 0-5. It is believed that the use of polymers in compositions according to the present invention can offset the otherwise deleterious effects of any solvent which is present when the product is used on certain plastics materials.
- solvent selected from the group comprising di-ethylene glycol mono n-butyl ether, mono-ethylene glycol mono n-butyl ether, propylene glycol n- butyl ether and mixtures thereof is present.
- solvent selected from the group comprising di-ethylene glycol mono n-butyl ether, mono-ethylene glycol mono n-butyl ether, propylene glycol n- butyl ether and mixtures thereof is present.
- effectively no solvent other than water is present.
- compositions contain either detergent builders or non-building metal ion sequesterants, collectively these are known as metal ion binding agents .
- Suitable metal ion binding agents include nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates especially polyphosphates, mixtures of ortho- and pyrophosphate, zeolites and mixtures thereof. Such agents can additionally function as abrasives if present in an amount in excess of their solubility in water as explained herein. In general, where the metal ion binding agent is a builder it will preferably will form from 0.05 to 25% by weight of the composition.
- Metal ion binding agents such as ethylenediaminetetraacetates (e.g. EDTA) , amino-polyphosphonates (e.g. those available as the 'DEQUEST' (TM) series of materials) and phosphates and a wide variety of other poly-functional organic acids and salts (including materials such as methyl glycine diacetate (MGDA) ) , can also optionally be employed.
- EDTA ethylenediaminetetraacetates
- amino-polyphosphonates e.g. those available as the 'DEQUEST' (TM) series of materials
- phosphates e.g. those available as the 'DEQUEST' (TM) series of materials
- TM 'DEQUEST'
- metal ion binding agents preferably organic acetates, more preferably MGDA or EDTA is believed to be that the microbiocidal properties of the cationic surfactants are improved especially against Gram- negative bacteria particularly under hard water conditions.
- Preferred levels of metal ion binding agents are 0.05-5%wt, preferably 0.1-3.0%wt, most preferably 1.5-3%wt.
- 1.5-3% of an organic acetate sequesterant will give a log five reduction in viable bacteria even against recalcitrant bacterial strains such as Pseudomomas aeruginosa .
- compositions according to the invention contain 1.5- 3%wt of MGDA or EDTA.
- the formulation containing polymer, alcohol, ethoxylate, cationic surfactant and sequestering agent has the additional benefit that it reduces the adhesion of fungal and/or bacterial spores to surfaces. This is described in further detail below with reference to examples. Minors
- composition according to the invention can contain other ingredients which aid in their cleaning performance and general utility.
- 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.
- suds regulating materials are organic solvents, hydrophobic silicas, silicone oils and hydrocarbons.
- An alternative suds regulating material comprises a mixed EO/PO nonionic surfactant.
- Suitable ethoxylated/propoxylated nonionic detergents include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide and propylene oxide, such as a coconut oil ethylene oxide/propylene oxide condensate having from 2 to 15 moles in total of ethylene oxide and propylene oxide per mole of coconut alcohol. It is preferable that the mole ratio of ethylene oxide to propylene oxide lies in the range 1:5-5:1.
- Particularly preferred ethoxylated/propoxylated nonionics include molecules of the general formula:
- R is an alkyl residue having an average carbon chain length of C8-C14, preferably C9-C11, EO is an ethylene oxide residue, n is 1-10, PO is a propylene oxide residue and m is 1-5.
- a particularly preferred material is C9-11 5-8EO 1-3PO, most preferably C9-11 6EO 2PO.
- the amount of ethoxylated/propoxylated nonionic detergent active to be employed in the composition of the invention will generally be from 2 to 10%wt, and most preferably from 3-6%wt.
- Preferred ratios of the ethoxylated to the ethoxylated/propoxylated surfactant fall into the range 4:1- 2 : 1 with the ethoxylated surfactant being present in weight excess over the ethoxylated/ propoxylated surfactant.
- compositions according to the invention can also contain, in addition to the ingredients already mentioned, other optional ingredients such as pH regulants, sunscreens, colourants, optical brighteners, soil suspending agents, enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, additional biocides, preservatives, detergent hydrotropes, perfumes and opacifiers.
- other optional ingredients such as pH regulants, sunscreens, colourants, optical brighteners, soil suspending agents, enzymes, compatible bleaching agents, gel-control agents, freeze-thaw stabilisers, additional biocides, preservatives, detergent hydrotropes, perfumes and opacifiers.
- Hydrotropes are useful optional components. It is believed that the use of hydrotropes enables the cloud point of the compositions to be raised without requiring the addition of anionic surfactants.
- Suitable hydrotropes include, alkali metal toluene sulphonates, urea, alkali metal xylene and cumene sulphonates, short chain, preferably C 2 -C 5 alcohols and glycols. Preferred amongst these hydrotropes are the sulphonates, particularly the cumene and toluene sulphonates .
- Typical levels of hydrotrope range from 0-5% for the sulphonates. Correspondingly higher levels of urea and alcohols are required. Hydrotropes are not generally required for dilute products.
- compositions of the invention effectively comprise a means for deposition of a surfactant/polymer complex at the surface being cleaned
- the compositions of the invention can further comprise components which it is desirable to deposit upon a surface.
- additional components are perfumes, non- cationic surfactant antimicrobial components and insect repellents and/or insecticides.
- compositions of the invention already comprise a cationic surfactant and are alkaline, some antimicrobial activity is already found in the compositions.
- Suitable additional non-cationic non-surfactant antimicrobial components are known in the art. Typical examples of this class of materials includes antimicrobial perfume oils and oil components.
- Typical levels of the non-cationic antimicrobial agent in formulations range from 0.01 to 8%, with levels of 0.05-4wt%, particularly around 2% being preferred for normal compositions and up to two or four times that concentration being present in so called, concentrated products.
- concentration of the antimicrobial agent will be in the range 0.05-0.5%wt.
- Particularly suitable insect repellents include essential oils such as those of genus Mentha, particularly Mentha arvensis, mentha piperita, Mentha spicata and Mentha cardica; Lemongrass East Indian oil, Lemon oil, Citronella, Cedarwood and Pine oil; terpenoids, particularly limonene, carvone, cineole, linalool, Gum Camphor, citronellal, alpha and beta terpenol, fencholic acid, borneol, iso borneol, bornyl acetate and iso bornyl acetate.
- the most preferred insect repellants are the terpenoids, particularly limonene.
- oils many are known to show antimicrobial effects as well as being insect repellents and/or perfumes.
- insect repellent required will vary with the nature of the material used. For essential oils and terpenoids, preferred levels are 0.1-5% on product.
- compositions of the present invention are essentially free of abrasive particles.
- the preferred pH of the neat products is 7-12 with a pH in the range of 7-11 being more preferred and a pH of around 10-11 being particularly preferred so as to balance cleaning and hygiene effectiveness.
- compositions according to the present invention are mobile aqueous liquids, having a pH of 7-12 (preferably 7-11) which comprise:
- a water soluble, anionic polymer having an average molecular weight less than 1,000,000, said polymer being a polymer of at least one of acrylic acid, methacrylic acid or maleic anhydride, with at least one of acrylic acid, methacrylic acid, maleic anhydride, ethylene, styrene and methyl vinyl ether, and ,
- a cationic surfactant which is a quaternary nitrogen compounds of the general formula R X R 2 R 3 R 4 N + X " , where Rl and R2 are the same or different C1-C4 alkyl or hydroxy alkyl, R3 is a C6-C22 alkyl, alkaryl or hydroxyalkyl, R4 is a C1-C22 alkyl, alkaryl or hydroxyalkyl and X is a monovalent anion equivalent, and,
- a solvent selected from the group comprising di-ethylene glycol mono n-butyl ether, mono- ethylene glycol mono n-butyl ether, propylene glycol n- butyl ether and mixtures thereof .
- compositions according to the invention are as described in the above paragraph but contain a cationic surfactant which has antimicrobial properties (such as benzalconium chloride) and a metal ion bing agent which is an organic acetate. These compositions exhibit improved primary and secondary cleaning at high pH as well as having effective and persistent antimicrobial properties against a broad range of microbes .
- compositions can be manufactured which comprise an essentially dry powder and which form the compositions of the invention on the addition of water.
- a specified level (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 a specified time at room temperature prior to cleaning. The initial effort required to clean the surface is referred to below as the primary cleaning effort.
- the DECAMEL sheets were pretreated with the test composition and copiously rinsed prior to soiling.
- the effort required to clean the re-soiled surfaces is known as the secondary cleaning effort.
- Formulations comprised nonionic surfactant and water with and without polymer and with and without cationic surfactant.
- the nonionic surfactants employed were DOBANOL 91-5 [TM] (C9- Cll alkyl, 5 EO alkyl ethoxylate ex. Shell) and DOBANOL 91-8 [TM] (C9-C11 alkyl, 8 EO alkyl ethoxylate ex. Shell) .
- the polymers illustrative of the present invention were a polyacrylic acid (VERSICOL Ell [TM] ex Allied Colloids) which had an average molecular weight of 250,000 Daltons.
- the cationic surfactants used were C n -alkyl trimethyl ammonium bromide (C n TAB: where n is 12,14 and 16), dicetyldimethyl and tricetylmethyl ammonium bromides (DTAB and TTAB respectively) .
- the pH of the compositions was regulated with sodium hydroxide or a carbonate/bicarbonate buffer system as indicated.
- Example la-Id in Table 1 below show the primary cleaning effort required using compositions which contained the formulations given, on the soil given above, aged for a period of two days after application of the soil at a coverage of 0.5mg/cm 2 .
- Table 2 below shows the effect of the cationic type on primary cleaning effort. Experiments were performed on the soil given above aged for a period of one day after application of the soil at a coverage of 0.25mg/cm 2 .
- Table 3 further illustrates the effect of pH for compositions which comprise 7% Dobanol 91-5 and 0.5% Versicol Ell in the presence of differing levels of CTAB at the pH indicated. pH was regulated with hydroxide and the experiments were performed on the soil given above aged for a period of one day after application of the soil at a coverage of 0.25mg/cm 2 . Results are given in total primary effort to clean in N/s.
- Table 4 provides additional data on the effect of pH for compositions which comprise 8% active in total and 0.5% Versicol Ell in the presence of differing levels of CTAB (C) and DTAB (D) at the pH indicated.
- the non-cationic active material is Dobanol 91-5. pH was regulated with hydroxide and the experiments were performed on the soil given above aged for a period of one day after application of the soil at a coverage of 0.25mg/cm 2 . Results are given in total primary cleaning effort in N/s.
- compositions show poor cleaning performance at the higher pH unless the cationic surfactant is present.
- the effect disclosed in WO 94/26858 is believed to be acting to reduce the primary cleaning effort requirement and there is no significant effect of adding cationic (if anything the compositions get slightly worse) although useful cleaning results are still attained.
- compositions comprise 7% of a mixture of Dobanol 91-5 and Dobanol 91-8, 1% CTAB and 0.5% Versicol Ell.
- the table lists the percentage of Dobanol 91-8 in the nonionic portion of the surfactant mixture, the remainder of the mixture being the Dobanol 91-5.
- compositions which are rich in the Dobanol 91-5 surfactant give the best reduction in primary cleaning effort, whereas while the compositions which are rich in Dobanol 91-8 (for example 5e) also give a useful reduction in primary cleaning effort this is less marked than for the other surfactant. It is clear from the table that the selection of an appropriate combination of surfactants enables the cloud point of the compositions to be controlled.
- Table 6 shows the effect on the secondary cleaning effort requirement in subsequent cleaning cycles for the compositions of the invention, using two different cationics.
- the 'VARI' material is Varisoft 442-100P (TM: ex. Sherex- Witco) a dihardened tallow dimethyl ammonium chloride.
- compositions of the present invention enable a reduction of both primary and secondary cleaning effort over a broad pH range.
- Table 7 shows the result of a biocidal efficacy test using the following bacteria (from the National Collection of Type Cultures or American Type Culture Collection) . Cultures were maintained on beads in a cryopreservative at -80/C.
- the culture suspensions were aseptically transferred into two 50ml centrifuge tubes and centrifuged at 2180g for 10 minutes (Mistral 1000, MSE) in order to harvest the cells.
- MSE Middle 1000
- the supernatants were poured off and the pellets resuspended in peptone diluent (0.1 percent peptone and 0.85 percent sodium chloride, pH 7.0).
- the suspensions were kept at 4/C until needed, and before use in the test were left on the bench at ambient temperature for at least 30 minutes.
- the test used was a microtitre plate assay, which is comparable to 'Method for the test for the antimicrobial activi ty of disinfectants in food hygiene ' , more commonly known as the European Suspension Test (EST) .
- Bovine albumin at a low level (0.03 percent) or a high level (0.3 percent) was included in some of the tests.
- a 1/15 dilution of the formulation was made in 'Water of Standard Hardness' as referred to in the above method.
- Microtitre plates (Bibby Sterilin, sterile 96-well, flat- bottom) were prepared by adding 270ml quenching solution in row B of each plate and 270ml peptone diluent into rows C-G.
- the quench solution was composed of Tween 80 (3.0 percent), lecithin (0.3 percent), L-histidine (0.1 percent), sodium thiosulphate (0.5 percent) and 0.25N KH 2 P0 4 buffer (1 percent) in sterile distilled water (1 litre) .
- Sterile distilled water or bovine albumin as appropriate 120ml was added to the test wells of row A.
- the formulation 150ml 1/15 dilution was added to the appropriate test wells.
- the formulations were randomised across the plates.
- the plates were placed on a stainless steel 'plate incubator' tray attached to a circulating waterbath, held at 20/C.
- formulations which contained Dobanol 91-8 (7wt percent) and polymer (VERSICOL Ell polyacrylic acid 0.5wt percent), and were adjusted to pHll. Formulations were diluted 1/20 in the presence of WSH (water of standard hardness) and 0.03% soil (bovine albumin) on final suspension. Examples are provided for formulations containing benzalkonium chloride (BAC) at both 1.0 and 2.0 wt%.
- WSH water of standard hardness
- soil bovine albumin
- Sequesterant either EDTA or MGDA was used as indicated in table 8.
- the test bacteria was Pseudomonas aeruginosa ATCC 15442, and assays were conducted as described above. Examples which give a log reduction greater than 5 are indicated in bold.
- formulations which contained Dobanol 91-8 (7wt percent) with and without polymer (VERSICOL Ell polyacrylic acid 0.5wt percent), and were adjusted to pHll.
- Formulations were diluted 1/20 in the presence of WSH (water of standard hardness) and 0.03% soil (bovine albumin) on final suspension. Examples are provided for formulations containing benzalkonium chloride (BAAC) at both 1.5 and 2.0 wt%. Sequesterant, either EDTA or MGDA was used as indicated in table 9.
- cleaning product (whether a formulation according to the invention, a control or a comparative example) was placed on a clean tile and carefully spread it over the whole tile surface using a flattened micropipette tip.
- the tile was allowed to dry in a 30°C incubator then any rinses were carried out by placing each tile in 100ml of sterile WSH for 30 seconds, removing and placing in a 30°C incubator to dry.
- each product was tested in duplicate, using 50 ⁇ l of sterile distilled water as the control formulation for control tiles.
- 50 ⁇ l of sterile distilled water as the control formulation for control tiles.
- tiles treated according to the present invention were inoculated together with a control tile with 20 ⁇ l of culture (as described above) so that there were approximately 2x10 ⁇ bacteria/tile in a 0.03% Bovine Albumin soil.
- the bacteria were spread over the whole tile area using a sterile spreader. After 30 minutes contact time between the bacteria and the tiles, a sterile microbiological cotton swab was wet with quench solution and swabbed thoroughly over the tile in two directions at right angles to each other.
- a column of wells in a sterile microtitre plate was inoculated with 270 ⁇ l of Peptone water, leaving the first well empty in each case.
- the first well was filled with 300 ⁇ l of the quenched swab solutions.
- a further 500 ⁇ l of quenched swab solution was plated directly onto an agar plate and spread using a sterile spreader. This plate is used for enumerating low levels of survivors.
- Serial 10-fold dilutions of the solutions were prepared by transferring 30 ⁇ l of solutions in row 1 to row 2; mixing them, then repeating the procedure down to row 6 so that a 10-6 dilution is achieved (pipette tips are changed between transfers) .
- results for such a test are shown in table 9 below: all composition contained soil and nonionic surfactant as noted above and the other components of the neat cleaning composition are indicated in the table. As noted above, log reductions are calculated relative to controls which had been treated with sterile water rather than a 'cleaning' composition. Table 9
- the example formulation (10a) contained Dobanol 91-8 (7%wt) with polymer (VERSICOL Ell polyacrylic acid 0.5%wt), cationic surfactant (2%wt BAAC) and sequesterant (2.5%wt MGDA) and was adjusted to pHll with NaOH. Comparative examples were also performed against Lysoform (TM) a commercially available disinfectant product.
- a suspension of Aspergillus niger spores (ATCC 6275) , prepared in sterile distilled water, was introduced to the plates (20ml per plate, 3 x 10 ⁇ spores/ml) . Plates were agitated in an orbital shaker to distribute spores evenly (1 min, 100 rpm) and left standing at room temperature for 30 min, before re-agitating (1 min, 100 rpm) . Supernatants were discarded and the plates allowed to dry. As the plates had been allowed to dry after pretreatment and prior to exposure to the spores, the spores had not been exposed to relatively high levels of the pre-treatment compositions. Initial attachment of spores to the treated and untreated plates could then be determined by the method given below.
- Results are given in table 10 below, a percentage of spores attached as compared with an untreated surface
- results show that for untreated surfaces rinsing and scrubbing remove some mould spores, but leave almost 40% of the spores on the surface even after scrubbing.
- results show that spores are less likely to attach to a surface treated with the compositions of the present invention, and, when spores do attach, they are not as strongly bound to the surface.
- compositions of the invention at least partly prevent the adhesion of spores to a surface and consequently, it is believed that the use of a composition according to the present invention would reduce the rate of regrowth on a clean surface of micro-organisms including moulds or bacteria which propogate through spores .
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9704989 | 1997-03-11 | ||
GBGB9704989.4A GB9704989D0 (en) | 1997-03-11 | 1997-03-11 | Improvements relating to hard-surface cleaning compositions |
PCT/EP1998/001273 WO1998040452A1 (en) | 1997-03-11 | 1998-02-24 | Hard-surface cleaning compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0971997A1 true EP0971997A1 (en) | 2000-01-19 |
EP0971997B1 EP0971997B1 (en) | 2003-07-23 |
Family
ID=10809027
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98912446A Expired - Lifetime EP0971997B1 (en) | 1997-03-11 | 1998-02-24 | Hard-surface cleaning compositions |
Country Status (18)
Country | Link |
---|---|
EP (1) | EP0971997B1 (en) |
JP (1) | JP2001514693A (en) |
KR (1) | KR20000076119A (en) |
CN (1) | CN1250470A (en) |
AU (1) | AU734919B2 (en) |
BR (1) | BR9808003A (en) |
CA (1) | CA2280877A1 (en) |
DE (1) | DE69816603T2 (en) |
ES (1) | ES2202825T3 (en) |
GB (1) | GB9704989D0 (en) |
HU (1) | HUP0001503A3 (en) |
ID (1) | ID22433A (en) |
IN (1) | IN190010B (en) |
MY (1) | MY120141A (en) |
PL (1) | PL187303B1 (en) |
TR (1) | TR199902201T2 (en) |
WO (1) | WO1998040452A1 (en) |
ZA (1) | ZA981574B (en) |
Cited By (4)
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US10323215B2 (en) | 2013-07-03 | 2019-06-18 | Basf Se | Solid polymer composition obtained by polymerization of an acid group containing monomer in the presence of a polyether compound |
US10555889B2 (en) | 2015-07-01 | 2020-02-11 | 3M Innovative Properties Company | Compositions for spore removal |
US11576845B2 (en) | 2017-01-04 | 2023-02-14 | 3M Innovative Properties Company | Methods of removing spores comprising alcohol, acrylate copolymer particles, and a cationic coated article |
US11634666B2 (en) | 2015-12-22 | 2023-04-25 | 3M Innovative Properties Company | Methods for spore removal comprising a polysorbate surfactant and cationic antimicrobial mixture |
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US6080387A (en) * | 1998-07-15 | 2000-06-27 | The Clorox Company | Aerosol antimicrobial compositions |
WO2000034423A1 (en) * | 1998-12-10 | 2000-06-15 | Unilever Plc | Detergent compositions |
DE19910788A1 (en) * | 1999-03-11 | 2000-09-14 | Cognis Deutschland Gmbh | Gel-shaped detergent for flush toilets |
AU2001253718A1 (en) * | 2000-04-20 | 2001-11-07 | Colgate-Palmolive Company | Toilet bowl cleaning compositions |
JP2002121593A (en) * | 2000-09-26 | 2002-04-26 | Spartan Chemical Co Inc | Sterilizing water-based composition for washing rigid surface and using method thereof |
GB0023898D0 (en) * | 2000-09-29 | 2000-11-15 | Reckitt Benckiser Inc | Improvements in or relating to organic compositions |
KR20040039615A (en) * | 2002-11-04 | 2004-05-12 | 애경산업(주) | Liquid cleasing composition having improved capacity for forming foam and low temperature stability |
KR20040051869A (en) * | 2002-12-13 | 2004-06-19 | 주식회사 엘지생활건강 | Composition of Liquid Cleaner having Excellent Viscosity and Detergency |
US7442679B2 (en) | 2004-04-15 | 2008-10-28 | Ecolab Inc. | Binding agent for solidification matrix comprising MGDA |
KR20050119490A (en) * | 2004-06-16 | 2005-12-21 | 애경산업(주) | Liquid detergent composition in the form of o/w microemulsion containing fabric softening agent |
JP5281420B2 (en) * | 2009-01-20 | 2013-09-04 | 花王株式会社 | Liquid detergent composition for hard surfaces |
WO2011142424A1 (en) * | 2010-05-14 | 2011-11-17 | ユケン工業株式会社 | Aqueous cleaning agent composition |
JP5536563B2 (en) * | 2010-06-28 | 2014-07-02 | 株式会社Adeka | Cleaning composition for dishwasher and cleaning method using the composition |
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EP2773739B1 (en) * | 2011-11-03 | 2015-11-04 | Unilever N.V. | A liquid hard surface antimicrobial cleaning composition |
FR2990364B1 (en) * | 2012-05-11 | 2014-06-13 | Commissariat Energie Atomique | METHOD FOR RADIOACTIVE DECONTAMINATION OF EARTH BY DISPERSE AIR FLOTATION FOAM AND FOAM |
CN102703247B (en) * | 2012-06-01 | 2014-06-18 | 句容市恒祥金属再生利用有限公司 | Dephosphorized cleaning agent for cleaning grinding wheel dust |
WO2014040869A1 (en) * | 2012-09-12 | 2014-03-20 | Unilever N.V. | Hard surface treatment composition |
WO2016196020A1 (en) * | 2015-05-29 | 2016-12-08 | 3M Innovative Properties Company | Enzyme cleaner for textiles with styrene maleic anhydride copolymers |
CN106701351A (en) * | 2015-11-12 | 2017-05-24 | 艺康美国股份有限公司 | Low-foaming vessel cleaning agent and mixed cationic/nonionic surfactant system for enhancing removal of oil-containing dirt |
BR112020004368A2 (en) | 2017-09-06 | 2020-09-08 | Basf Se | active washing and cleaning polymer film, process for producing an active washing and cleaning polymer film, use of a polymer film, cover or coating for a portion of detergent or cleaner, and, detergent or cleaner |
JP7170300B2 (en) * | 2017-12-11 | 2022-11-14 | 株式会社ニイタカ | liquid detergent composition |
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JPH01250473A (en) * | 1988-03-31 | 1989-10-05 | Lion Corp | Liquid softening agent composition |
EP0379544A1 (en) * | 1988-06-21 | 1990-08-01 | Vax Appliances Limited | Fabric cleaning and sanitizing compositions |
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CZ174497A3 (en) * | 1994-12-09 | 1998-06-17 | Unilever N. V. | Cleansing agent |
-
1997
- 1997-03-11 GB GBGB9704989.4A patent/GB9704989D0/en active Pending
-
1998
- 1998-02-24 AU AU67280/98A patent/AU734919B2/en not_active Ceased
- 1998-02-24 BR BR9808003-2A patent/BR9808003A/en not_active Application Discontinuation
- 1998-02-24 CN CN98803209A patent/CN1250470A/en active Pending
- 1998-02-24 WO PCT/EP1998/001273 patent/WO1998040452A1/en active IP Right Grant
- 1998-02-24 JP JP53918698A patent/JP2001514693A/en not_active Ceased
- 1998-02-24 TR TR1999/02201T patent/TR199902201T2/en unknown
- 1998-02-24 KR KR1019997008208A patent/KR20000076119A/en not_active Application Discontinuation
- 1998-02-24 CA CA002280877A patent/CA2280877A1/en not_active Abandoned
- 1998-02-24 ES ES98912446T patent/ES2202825T3/en not_active Expired - Lifetime
- 1998-02-24 HU HU0001503A patent/HUP0001503A3/en unknown
- 1998-02-24 PL PL98335609A patent/PL187303B1/en not_active IP Right Cessation
- 1998-02-24 DE DE69816603T patent/DE69816603T2/en not_active Expired - Fee Related
- 1998-02-24 EP EP98912446A patent/EP0971997B1/en not_active Expired - Lifetime
- 1998-02-24 ID IDW991001A patent/ID22433A/en unknown
- 1998-02-25 ZA ZA9801574A patent/ZA981574B/en unknown
- 1998-02-26 IN IN101BO1998 patent/IN190010B/en unknown
- 1998-03-09 MY MYPI98001010A patent/MY120141A/en unknown
Non-Patent Citations (1)
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10323215B2 (en) | 2013-07-03 | 2019-06-18 | Basf Se | Solid polymer composition obtained by polymerization of an acid group containing monomer in the presence of a polyether compound |
US10344249B2 (en) | 2013-07-03 | 2019-07-09 | Basf Se | Gel-like polymer composition obtained by polymerizing a monomer containing acid groups in the presence of a polyether compound |
US10647945B2 (en) | 2013-07-03 | 2020-05-12 | Basf Se | Use of a gel-like polymer composition which can be obtained by polymerizing an acid group-containing monomer in the presence of a polyether compound in formulations for automatic dishwashing |
US10655088B2 (en) | 2013-07-03 | 2020-05-19 | Basf Se | Solid polymer composition obtained by polymerization of an acid group-containing monomer in the presence of a polyether compound |
US10555889B2 (en) | 2015-07-01 | 2020-02-11 | 3M Innovative Properties Company | Compositions for spore removal |
US11634666B2 (en) | 2015-12-22 | 2023-04-25 | 3M Innovative Properties Company | Methods for spore removal comprising a polysorbate surfactant and cationic antimicrobial mixture |
US11576845B2 (en) | 2017-01-04 | 2023-02-14 | 3M Innovative Properties Company | Methods of removing spores comprising alcohol, acrylate copolymer particles, and a cationic coated article |
Also Published As
Publication number | Publication date |
---|---|
ES2202825T3 (en) | 2004-04-01 |
JP2001514693A (en) | 2001-09-11 |
PL187303B1 (en) | 2004-06-30 |
PL335609A1 (en) | 2000-05-08 |
DE69816603D1 (en) | 2003-08-28 |
HUP0001503A2 (en) | 2000-09-28 |
AU6728098A (en) | 1998-09-29 |
DE69816603T2 (en) | 2004-06-09 |
EP0971997B1 (en) | 2003-07-23 |
GB9704989D0 (en) | 1997-04-30 |
WO1998040452A1 (en) | 1998-09-17 |
IN190010B (en) | 2003-05-31 |
CA2280877A1 (en) | 1998-09-17 |
AU734919B2 (en) | 2001-06-28 |
TR199902201T2 (en) | 2000-05-22 |
ZA981574B (en) | 1999-08-25 |
KR20000076119A (en) | 2000-12-26 |
CN1250470A (en) | 2000-04-12 |
BR9808003A (en) | 2000-03-08 |
HUP0001503A3 (en) | 2003-02-28 |
ID22433A (en) | 1999-10-14 |
MY120141A (en) | 2005-09-30 |
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