AU3249599A - Hard surface cleaners - Google Patents

Description

WO 99/36499 PCTIEP99/00246 HARD SURFACE CLEANERS 5 Field of the Invention The present invention relates to hard surface cleaning compositions which contain a UV absorbing agent. 10 Background to the Invention Many household fittings fixtures and furnishings suffer from the harmful effects of the suns rays. This can, for example 15 lead to discoloration of curtains, furniture (leather and wooden) and wooden floors. It is believed that a significant part of this damage is caused by the UV components of the sunlight, particularly in the UV-B region (280-320 nm) range. Similar problems are encountered in 20 office and institutional environments although the present invention will be described with particular reference to household environments. It is known to protect textiles from UV radiation by 25 treating them with a UV absorbing agent. For example, EP697481 (CIBA-GEIGY: 1995) concerns textile treatment with a composition comprising UV-A compound, emulsifying agent, water and polysiloxane (i.e. silicone) in an otherwise aqueous textile treatment composition which comprises: 30 a) a non-reactive UVA compound b) an emulsifying or dispersing agent for the UVA compound WO99/36499 PCT/EP99/00246 -2 c) water d) optionally, a polysiloxane based product. 5 Broad-spectrum UV absorbing agents, such as benzophenone derivatives, can be difficult to incorporate in compositions due to their insolubility, cross-reaction with other components etc. As noted above it is known to overcome this problem by putting UV absorbing agents into products which 10 are in the form of oily emulsions. Single phase or at least non-macro-emulsion liquid products are preferred to macro emulsions for reasons of product stability and appearance. An additional problem is that of substantivity. Whereas it is to be expected that a fabric will be easy to treat due to 15 its tendency to adsorb liquids formulation of hard surface cleaning compositions is more difficult due to the tendency of these formulations to remove a benefit agent from the surface as rapidly as it is deposited. Consequently there is a need to provide new formulations for hard surface cleaning 20 compositions which contain UV absorbing agents. Brief Description of the Invention 25 We have determined that the aforementioned difficulties can be overcome by incorporating the UV absorbing agent in a hard-surface cleaning composition which also contains a polymer. It is believed that the use of such a composition will leave sufficient UV-absorber on the surface being 30 cleaned to reduce the damaging effect of UV light illuminating the said surface. Accordingly, a first aspect of the present invention relates to a hard-surface cleaning composition comprising: 35 WO99/36499 PCT/EP99/00246 -3 a) 0.1-50% of a nonionic surfactant, b) 0.005-5% of a water soluble, anionic polymer having an average molecular weight of less than 1,000,000, 5 wherein, the ratio of polymer:nonionic is 0.1:1 or less, and c) 0.01-5wt% of a UV-absorbing agent, 10 (All percentages mentioned herein are by weight of the total composition, unless indicated otherwise.) A second aspect of the present invention relates to a method of reducing UV damage to hard surfaces which comprises the 15 step of treating the surface with a cleaning composition as described above. It is believed that the presence of the polymer improves the deposition of the UV absorbing agent at the surface being 20 cleaned. Detailed Description of the Invention 25 Typically, the UV absorbing agent is effective in the UV-B range, i.e. it shows significant adsorbance in the 280-320 nm wavelength range. Preferably, the UV absorbing agent is a benzophenone derivative. More preferably the UV absorbing agent is 2-hydroxy-4-methoxybenzophenone (benzophenone-3). 30 Suitable materials are available in the marketplace from BASF and Haarmann & Reimer (H&R). Alternative UV absorbers believed suitable for use in the compositions of the present invention include 35 methoxycinnamic acid esters such as octyl methoxycinnamate WO99/36499 PCT/EP99/00246 -4 and also particularly phenylbenzimidazole sulfonic acid. Many laundry detergent compositions comprise so called optical whiteners or brighteners, i.e. fluorescent compounds which absorb UV light and re-emit this as visible, 5 particularly blue, light. Such compounds have no use in the hard surface cleaning compositions of the present invention and are therefore not comprised in the term 'UV absorbing agent' and UV absorber. 10 Suitable levels of UV absorbing agents are from 0.01%wt upwards, preferably at least 0.05%, more preferably at least 0.08%. Higher amounts than 2%wt rarely serve a useful purpose and the amounts are preferably at most 1%, more preferably at most 0.5%. 15 While the pH of the composition can fall in the range 1.0 12, it is preferable that the pH of the composition is not below 2.0, most preferably not below 3.0. Above pH 8.5 the benefit of some UV absorbers falls off, other UV absorbers 20 such as phenylbenzimidazole sulfonic acid may succesfully be used up to pH 12. Below pH 3.0 damage to the hard surface may occur, especially to enamel surfaces. The most preferred pH is from around 3.0 to 8.5 for compositions according to the present invention. Compositions having a pH of around 4 25 do not require the presence of a cationic surfactant. At higher pH's a cationic surfactant may be useful to stabilize the product. A base such as sodium hydroxide or ammonia and/or an acid such as citric acid are generally used to bring the pH to the required level. 30 Advantageously, the compositions of the invention are aqueous and are preferably not macroscopic emulsions. Other preferred components of formulations according to the invention are described in greater detail below. 35 WO99/36499 PCT/EP99/00246 -5 Surfactants: 5 It is essential that the compositions of the present invention comprise at least one nonionic surfactant component, preferably in an amount of 1-30%wt. Of the nonionic surfactants alkoxylated alcohols, alkoxylated 10 phenols, alkyl-polyglucoside (APG) and amine oxides are very suitable for use in the compositions of the present invention e.g. in amounts of 0.1-5%wt. In certain compositions according to the invention APG is 15 preferred for its non-streaking and good foaming properties. Preferred levels of APG are such that the composition comprises 0.1-5%wt of APG, preferably 0.1-3 %wt, most preferably 0.2-2 %wt. Preferred APGs contain C8-C16 alkyl chains and it is preferred that more than 50%wt of the APG 20 present in the compositions of the invention comprises C12 C14 alkyl APG and that the majority of the remaining APG contains C8-C16. The preferred degree of polymerization is 1.1-1.6, more preferably 1.3-1.5. Suitable materials include GLUCOPON 425 CS TM (ex HENKEL). 25 Other suitable nonionics, as mentioned above, are alkoxylated alcohols, alkoxylated alkyl-phenols or amine oxides. Of these, alkoxylated alcohols are preferred as surfactants. Suitable nonionic detergent active compounds 30 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 WO99/36499 PCT/EP99/00246 -6 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. Ethoxylated aliphatic alcohols are 5 particularly preferred. Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with 10 ethylene oxide, such as a coconut alcohol ethylene oxide condensate having from 1 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 1 to 25 moles of ethylene oxide per mole of alkylphenol. 15 Particularly preferred nonionic surfactants include the condensation products of C8-C18 alcohols with 2-12 moles of ethylene oxide. The most preferred alkoxylated alcohol nonionic surfactants are ethoxylated alcohols having a chain 20 length of C9-C11 and an EO value of at least 5 but less than 10. Particularly preferred nonionic surfactants include the condensation products of C10 alcohols with 5-8 moles of ethylene oxide. 25 The preferred ethoxylated alcohols have a calculated HLB of 10-16. While mixtures of nonionic surfactants can be used it is preferred to use a single commercially available surfactant. 30 Further surfactant components may be selected from the cationic and/or amphoteric surfactant materials. Cationic surfactants can be included in the compositions of the invention as hygiene agents, or to assist in the 35 solubilisation of the polymer at high pH's as mentioned WO99/36499 PCT/EP99/00246 - 7 above. Typically the cationic surfactants are quaternary ammonium salts of the general formula RlR 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 5 alkyl, alkaryl or hydroxyalkyl, at least one of the radicals R1-R4 is a Cl-C4 alkyl or hydroxy alkyl and X is a monovalent anion equivalent. The cationic surfactants are preferably the quaternary 10 nitrogen compounds wherein R1 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. Preferably X is a halogen, most preferably chloride or 15 bromide. Preferably R1 and R2 are methyl. In embodiments of the invention R3 is preferably C8-C18 alkyl, more preferably C10 C16 alkyl. In embodiments of the invention R4 is preferably 20 methyl, C8-C18 alkyl or benzyl. Thus, 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 25 hydrocarbons or contain aromatic rings. A further advantage of including a cationic surfactant in the compositions of the invention is that preferred cationic surfactants confer antimicrobial properties on the formulation. Surprisingly, we have determined that 30 compositions according to the invention which contain antimicrobial cationic surfactants show longer lasting hygiene on surfaces which have been treated with the compositions.

WO99/36499 PCTIEP99/00246 -8 Particularly suitable cationic detergent-active compounds include cetyltrimethyl ammonium bromide (CTAB), hardened di tallow-dimethyl-ammonium chloride (available in the marketplace as BARDAC 2250), benzalkonium chloride and 5 mixtures thereof. The cationic surfactants which comprise one aryl substituent are especially preferred as they are believed to give particularly good antimicrobial effects. 10 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. 15 Without wishing to limit the present invention by reference to any theory of operation it is believed that enhanced detergency of nonionic surfactants, at acid pH, in the presence of polymer is due to the formation of a hydrogen bonded complex between the nonionic surfactant and the 20 uncharged, undissociated carboxylic acid groups of the polymer. As the pH is raised, the acid groups of the polymer dissociate and the hydrogen-bonded complex is no longer formed. It is believed that in the presence of the cationic surfactant required by some embodiments of the present 25 invention, negatively charged (i.e. carboxylic dissociated) polymer can interact with the cationic surfactant and the nonionic surfactant to form a three-component complex which deposit the nonionic surfactant upon the soil and/or surface being cleaned. While the mechanism is not entirely clear, 30 this may possibly be due to the interaction of the charged polymer with mixed miscelles of cationic and nonionic surfactant. It is believed that the deposition of the complex on the 35 surface has two results. Firstly the concentration of the WO99/36499 PCT/EP99/00246 -9 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 5 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. 10 Optionally, the composition can include one or more amphoteric surfactants, preferably betaines, or other surfactants such as amine-oxide and alkyl-amino-glycinates. Betaines are preferred for reasons of cost, low toxicity and wide availability. It is believed that amphoteric surfactants 15 show a slight synergy with some organic acids (when present) as regards antimicrobial effects. Preferably the overall level of surfactant in the compositions of the invention is 0.1-10%wt, more preferably 20 0.5-8%wt, most preferably 0.5-4%wt. 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 25 below some 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 other than those mentioned above. 30 Polymers: As noted above the polymers according to the invention are 35 water soluble polymers having an average molecular weight of WO99/36499 PCT/EP99/00246 - 10 less than 1,000,000. Typically, these polymers are polymers bearing carboxylate functional groups although the use of other anionic polymers is possible. In the context of the present invention, anionic polymers are those which are 5 capable of carrying a negative charge or such 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 10 marketplace. Particularly useful 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, 15 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 20 vinyl ether and ethylene. Preferably, the average 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-11 TM (ex. Allied 25 Colloids) which is a polyacrylic acid, has been found to be a suitable polymer for use in compositions according to the invention. Typically, the surfactant based cleaning compositions 30 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 WO 99/36499 PCTIEP99/00246 - 11 in applications of the invention where considerable dilution is expected, such as in floor cleaning. Preferably the level of polymer is 0.05-4.0wt% at which level 5 the anti-resoiling benefits become particularly significant. More preferably at least 0.1wt% of polymer is present, most preferably at least 0.2%wt. We have determined that higher levels of polymer than 3%wt or even 2%wt do not give significant further cleaning advantages taking common 10 dilution factors into account, 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. However, for very concentrated products which are strongly diluted prior to 15 use, the initial polymer level can be as high as 5%wt. As mentioned above, 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 20 polymer is reduced. Solvents: 25 One or more solvents may be present in the compositions of the invention. The presence of solvents is often beneficial. It is preferred that the compositions of the present 30 invention comprise not more than 25%wt of glycol ether or alkanol solvents of the general formula: R1-0-(EO)m-(PO)n-R2, 35 wherein R1 and R2 are independently Cl-C6 alkyl or H, but WO99/36499 PCT/EP99/00246 - 12 not both hydrogen, m and n are independently 0-5, E stands for an ethylene group and P stands for a propylene group. The alcohol solvents are selected from the Cl-C6 5 branched or straight chain alkanols, more preferably one or more of methanol, ethanol, propanols or butanols. Ethanol and iso-propanol are particularly preferred. Preferably, the solvent comprises at least one glycol ether 10 solvent selected from the group comprising diethylene glycol mono-n-butyl ether (available in the marketplace as Butyl Digol TM), ethylene glycol mono-n-butyl ether and propylene glycol mono-n-butyl ether and mixtures thereof. The total level of these solvents in the detergent 15 compositions prepared according to the invention is preferably not more than 25% by weight, more preferably 20% or less, most preferably 10% or less. on the other hand the compositions preferably contain at least l%wt of these solvents, more preferably at least 2% and most 20 preferably at least 5%. Antimicrobials: 25 Optionally antimicrobial agents can be used in the compositions of the present invention. The preferred antimicrobials are the quaternary ammonium compounds mentioned above and/or phenolic compounds. 30 Typical levels of the antimicrobial agent in formulations range from 0.01 to 8%wt, 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. Although 35 both the normal and concentrated products can be used neat it WO99/36499 PCT/EP99/00246 - 13 will be commonplace for these to be diluted by the user before use. For sprayable products, which are seldom diluted prior to use, the concentration of the antimicrobial agent will be in the range 0.05-0.5%wt. 5 In general, whatever the strength of the product the ratio of the nonionic surfactant to the antimicrobial agent will preferably be in the range 50:1 to >1:1, more preferably 30:1 to >1:1 i.e. an excess of nonionic will be present relative 10 to the antimicrobial. Where antimicrobial agents are not present at significant levels it is advantageous that the compositions comprise a preservative. A suitable preservative is PROXEL LV T m or 15 FORMOL T M . Insect Repellent Materials: 20 Given that the compositions of the invention effectively comprise a means for deposition of a surfactant/polymer complex at the surface being cleaned, it is envisaged that the compositions of the invention can further comprise components which it is desirable to deposit upon a surface. 25 A preferred class of additional components is insect repellent materials. Particularly suitable insect repellents include essential oils such as those of genus Mentha, particularly Mentha 30 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 WO99/36499 PCT/EP99/00246 - 14 acetate and iso-bornyl acetate. The most preferred insect repellents are the terpenoids, particularly limonene. Of the above mentioned oils many are known to show antimicrobial effects as well as being insect repellents and/or perfumes 5 and can therefore perform more than one function. The level of 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. 10 Minors and Optional Components: The compositions according to the invention can contain other 15 minor ingredients which are not essential, but aid in their cleaning performance and in maintaining the physical and chemical stability of the product. For example, the composition can contain detergent builders. 20 In general, a builder, when employed, preferably will form from 0.1 to 25% by weight of the composition. Metal ion sequestrants, including ethylenediamine tetraacetates, aminopolyphosphonates (such as those in the 25 DEQUEST range) and phosphates and a wide variety of other poly-functional organic acids and salts, can also optionally be employed. It is believed that the hygiene performance of a composition is improved by the presence of a metal ion sequesterant. 30 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. The presence of both anionic surfactants 35 and betaine at the same time is believed to be less desirable WO99/36499 PCT/EP99/00246 - 15 as these surfactants interact and form a complex which inhibits the synergistic hygiene activity of the amphoterics with the organic acid. Preferably the formations according to the invention are free of anionic surfactants when betaine is 5 present, or contain low levels of anionic surfactants, i.e. less than 50% of the total weight of surfactant present and preferably less than 50% of the weight of the betaine in the product. Anionics are compatible with the solely alcohol ethoxylate based compositions of the present invention when 10 the level is below 50%wt of the total surfactant present, but their level should be minimized in view of their interaction with the polymers. Preferably the level of anionic is below 30%wt of the total surfactant content of the composition and more preferably below 10% of the surfactant content. It is 15 possible to make compositions which contain little or no anionic surfactant. Suitable hydrotropes include, alkali metal toluene sulphonates, urea, alkali metal xylene and cumene 20 sulphonates, polyglycols, >20EO ethoxylated alcohols, short chain, preferably C2-C5 alcohols and glycols. Preferred amongst these hydrotropes are the sulphonates, particularly the cumene, xylene and toluene sulphonates. For the purposes of this invention the aromatic sulphonate hydrotropes are non 25 considered anionics. Typical levels of hydrotrope range from 0-5% for the sulphonates. Correspondingly higher levels of urea and alcohols are required. Hydrotropes are not always required 30 for dilute, sprayable products, but may be required if lower EO or longer alkyl ethoxylates are used or the cloud point needs to be raised considerably. Typically, the cloud point of the final composition should preferably be in the range 45-50 0 C. The cumene sulphonate is the most preferred 35 hydrotrope. For ethoxylated nonionic levels of around 7%wt WO99/36499 PCTIEP99/00246 - 16 corresponding levels of SCS will generally be in the range 0.6-0.8wt%, whereas for ethoxylated nonionic levels of around 14%wt corresponding levels of SCS will generally be in the range 1.0-1.2wt%. 5 Typically, 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 10 use. One example of 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 C8-C24 fatty acids, and preferably C10-C20. Particularly useful are the sodium and potassium and mono-, 15 di- and tri-ethanolamine salts of the mixtures of fatty acids derived from coconut oil and ground nut oil. When employed, the amount of soap can form at least 0.005%, preferably 0.5% - 2% by weight of the composition. 20 Further examples of suds regulating materials are organic solvents, hydrophobic silicas, silicone oils and hydrocarbons. An alternative suds regulating material comprises a mixed 25 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 30 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 in these condensation products lies in the range 1:5-5:1. 35 WO99/36499 PCT/EP99/00246 - 17 Particularly preferred ethoxylated/propoxylated nonionics include molecules of the general formula: RO(EO)n(PO)mH 5 wherein: 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 has C9-C11, 5-8E0, 1 10 3PO, most preferably C9-C11, 6EO, 2PO. The amount of ethoxylated/propoxylated nonionic detergent active to be employed in the composition of the invention will generally be 2-10%wt, and most preferably 3-6%wt. 15 Preferred weight ratios of the ethoxylated to the ethoxylated/propoxylated surfactant in the composition fall in the range 4:1 - 2:1, with the ethoxylated surfactant being present in weight excess over the ethoxylated/ propoxylated 20 surfactant. Bleaching compounds generally serve no useful purpose in cleaning compositions of the present invention and will therefore normally be absent. Also, the presence of 25 abrasives is difficultly reconcilable with the purposes of the present invention. Moreover such components and other water-insoluble solid inorganic compounds tend to leave difficultly removable traces on a surface. They will, therefore, normally be absent as well. 30 Preferred Composition: Preferred compositions according to the present invention WO99/36499 PCT/EP99/00246 - 18 have a pH of 3-8 and comprise: a) 1-10%wt of 2-15EO ethoxylated C8-C18 alcohol nonionic surfactant, 5 b) 0.1-4%wt of a water soluble, anionic polymer having an average molecular weight less than 1,000,000, said polymer being a (co)polymer of at least one of acrylic acid, methacrylic acid or maleic anhydride, with at 10 least one of acrylic acid, methacrylic acid, maleic anhydride, ethylene, styrene and methyl vinyl ether, c) 0.01-1%wt of a UVA-B absorbing material, preferably a benzophenone derivative 15 d) less than 1%wt of anionic surfactants, and, e) 0.1-4%wt of a hydrotrope 20 Alternative preferred compositions are set out as compositions A and B below. A% B% Nonionic (Dobanol 91.5) 7.0 14.0 Nonionic EO/PO (BIODAC L6S50) 3.0 6.0 Polyacrylate (Versicol Ell) 0.5 1.0 UV absorbing agent (Benzophenone-3) 0.01-1 0.01-1 Coco Fatty Acid 0.5 1.0 Citric acid 0.6 1.2 Sodium Hydroxide -- to pH 3.75 - Sodium Cumene Sulphonate -- to cp 45-50 - Preservative (Proxel LV) 0.016 0.016 Perfume 0.38-0.5 0.76-1.0 Water qv qv Viscosity (mPas) 20 80 WO99/36499 PCT/EP99/00246 - 19 Compositions can also be manufactured which are essentially dry powders and which form the compositions of the invention on addition of water. 5 In order that the present invention may be further understood it will be described hereinafter by way of example: 10 Examples In order to demonstrate the effectiveness of the present invention compositions according to the invention were compared with products which were available in the Brazilian 15 market. A typical heavy duty cleaners in this market is 'Veja T M , available from Reckitt & Colman. A further known product is 'Domex TM and is manufactured by Lever. 20 Example 1: UV adsorbance The compatibility of the UV absorber Benzophenone-3 of H&R with Veja was tested by simple mixture. Since the pH of this product is high, it was expected that the absorber will show 25 a degree of incompatibility. The Lever product, Domex has a pH of around 4. It is therefore expected to be more compatible with the UV absorber. For comparative purposes a product (Comparative) was used as given in table 1 below: 30 Table 1 Raw Material w/w (%) Butyl Digol 9.00 Ethanol 10.00 WO99/36499 PCTIEP99/00246 - 20 Glucopon 425 CS 0.80 Dye trace Water to 100 The Domex product was formulated as follows: 5 Table 2 Raw Material Iw/w (%) Nonionic 6EO 3.0 wt% (surfactant) Sodium Cumene Sulphate 1.8 wt% (hydrotrope) Versicol E-11 0.25 wt% (cleaning aid, deposition aid) Sodium Hydroxide 0.04 wt% (pH regulator) Proxel 0.02 wt% (preservative) Perfume 1.0 wt% Dyestuff 0.00102 wt% Benzophenone-3 0.01 to 1% (UVA-B absorber) Water to 100% In the above exemplary formulation the order of addition is important, since the UV absorbing material is difficult to 10 dissolve in water. In the example a pre-mixture of the UV absorber in solvent is prepared and the remaining components are admixed before the UV absorber/solvent is added. In the case of the comparative formulation (Comp) a pre-mixture of UV absorber/Butyl Digol at 10% concentration (0.5 g UV 15 absorber in 5 g Butyl Digol) was added after all the other components to give a final product concentration of 0.01 1%. UV light absorbance was measured with a spectrophotometer. 20 Table 3 shows the results. Table 3 WO99/36499 PCT/EP99/00246 - 21 Comp Veja + UV Domex + UV adsorbance% at (nm) 280 1.439 13.838 11.76 290 0.905 12.724 13.95 300 0.382 10.161 12.99 310 0.153 7.806 12.1 320 0.08 7.07 12.13 330 0.08 6.9 10.85 340 0.09 6.29 7.57 The measurements in Table 3 clearly show the effectiveness 5 of this absorber in Domex, and a decrease in absorbance and hence less effectiveness for the Veja product (which does not contain polymer and has a higher pH). In addition visual clues as to discoloration of the product indicated a degree of incompatibility of the absorber and the Vega product. It 10 can be seen that the comparative product (comp) which did not contain the absorbing material had little or no UV adsorbance. 15 Example 2: cleaning performance: In order to demonstrate that the products according to the 20 invention were effective cleaners cleaning effort was measured for the preferred product of the invention and an embodiment prepared by mixing Vega with the Benzophenone-3 UV absorber. Results are given in table 4 below, in terms of the effort (in N.s) needed to clean a surface, either 25 Formica T M or enamel which had been soiled in a standard manner.

WO99/36499 PCT/EP99/00246 - 22 Table 4 Veja Domex Formica/fatty 201 116 soil Enamel/fatty soil 246 218 5 From the above examples it can be seen that the preferred compositions of the invention are both effective cleaners and effectively reduce UV exposure of surfaces which have 10 been treated with them.

Claims (7)

1. 2. Composition according to claim 1 wherein the polymer is a polymer of acrylic or methacrylic acid or maleic anhydride, or a co-polymer of one or more of the same 20 either together or with other monomers.
2. 3. Composition according to claim 2 wherein the polymer is selected from the group comprising polyacrylic acid, polymaleic anhydride and copolymers of either of the 25 aforementioned with ethylene, styrene and methyl vinyl ether.
3. 4. Composition according to claims 1-3 which further comprises 0.005-5%wt of a cationic surfactant. 30
4. 5. Composition according to claims 1-4 having a pH of 3-12. 35 WO99/36499 PCT/EP99/00246 - 24 6. Composition according to claim 1-5 which further comprises a glycol ether or alkanol solvent of the general formula: 5 Rl-0-(EO0)m-(PO)n-R2, wherein R1 and R2 are independently C1-6 alkyl or H, but not both hydrogen, m and n are independently 0-5. 10
5. 7. Composition according to claims 1-6 wherein the UV absorbing agent comprises a benzophenone derivative.
6. 8. Composition according to claim 7 which comprises 15 2-hydroxy-4-methoxybenzophenone.
7. 9. Composition according to claim 7 which comprises phenylbenzimidazole sulphonic acid. 20 10. A method of reducing UV damage to hard surfaces which comprises the step of treating the surface with a cleaning composition according to any one of claims 1-9. 25