WO1999036499A1 - Hard surface cleaners - Google Patents

Hard surface cleaners Download PDF

Info

Publication number
WO1999036499A1
WO1999036499A1 PCT/EP1999/000246 EP9900246W WO9936499A1 WO 1999036499 A1 WO1999036499 A1 WO 1999036499A1 EP 9900246 W EP9900246 W EP 9900246W WO 9936499 A1 WO9936499 A1 WO 9936499A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
composition according
compositions
surfactant
preferred
Prior art date
Application number
PCT/EP1999/000246
Other languages
French (fr)
Inventor
Marcia Regina Domingues Mobaier
Robert Jan Reinier Uhlhorn
Original Assignee
Unilever N.V.
Unilever Plc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Priority to JP2000540204A priority Critical patent/JP2002509186A/en
Priority to HU0100524A priority patent/HUP0100524A3/en
Priority to AU32495/99A priority patent/AU3249599A/en
Priority to CA002317544A priority patent/CA2317544A1/en
Priority to EP99930894A priority patent/EP1049762A1/en
Publication of WO1999036499A1 publication Critical patent/WO1999036499A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2072Aldehydes-ketones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/835Mixtures of non-ionic with cationic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/28Heterocyclic compounds containing nitrogen in the ring
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to hard surface cleaning compositions which contain a UV absorbing agent .
  • 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:
  • UV absorbing agents such as benzophenone derivatives
  • 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 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 compositions which contain UV absorbing agents.
  • a first aspect of the present invention relates to a hard-surface cleaning composition
  • a hard-surface cleaning composition comprising: a) 0.1-50% of a nonionic surfactant,
  • a second aspect of the present invention relates to a method of reducing UV damage to hard surfaces which comprises the step of treating the surface with a cleaning composition as described above .
  • the presence of the polymer improves the deposition of the UV absorbing agent at the surface being cleaned.
  • the UV absorbing agent is effective in the UV-B range, i.e. it shows significant adsorbance in the 280-320 nm wavelength range.
  • the UV absorbing agent is a benzophenone derivative. More preferably the UV absorbing agent is 2-hydroxy-4-methoxybenzophenone (benzophenone-3) .
  • Suitable materials are available in the marketplace from BASF and Haarmann & Reimer (H&R) .
  • UV absorbers believed suitable for use in the compositions of the present invention include methoxycinnamic acid esters such as octyl methoxycinnamate 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, 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 .
  • 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%.
  • 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 such as phenylbenzimidazole sulfonic acid may successivefully 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 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 .
  • 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.
  • compositions of the present invention comprise at least one nonionic surfactant component, preferably in an amount of l-30%wt.
  • nonionic surfactants alkoxylated alcohols, alkoxylated 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.
  • APG is 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 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
  • nonionics are alkoxylated alcohols, alkoxylated alkyl-phenols or amine oxides. Of these, alkoxylated alcohols are preferred as surfactants.
  • 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. Ethoxylated aliphatic alcohols are 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 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 .
  • 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 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 CIO alcohols with 5-8 moles of ethylene oxide .
  • 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 .
  • 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 solubilisation of the polymer at high pH's as mentioned above.
  • the cationic surfactants are quaternary ammonium salts of the general formula R ⁇ 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 monovalent anion equivalent .
  • the cationic surfactants are preferably the quaternary nitrogen compounds wherein 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- C16 alkyl.
  • R4 is preferably methyl, C8-C18 alkyl or benzyl.
  • 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.
  • 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.
  • preferred cationic surfactants confer antimicrobial properties on the formulation.
  • 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 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.
  • 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, this may possibly be due to the interaction of the charged polymer with mixed miscelles of cationic and nonionic surfactant .
  • 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 1 cleaning effort.
  • the composition can include one or more amphoteric surfactants, preferably betaines, or other surfactants such as amine-oxide and alkyl-amino-glycinates .
  • 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 show a slight synergy with some organic acids (when present) as regards antimicrobial effects.
  • the overall level of surfactant in the compositions of the invention is 0.1-10%wt, more preferably 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 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.
  • the polymers according to the invention are water soluble polymers having an average molecular weight of 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 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 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, 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 average molecular weight of the polymer is at least 5000, more preferably at least 50,000 and most
  • TM preferably in excess of 100,000.
  • VERSICOL E-ll (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 0.05-4.0wt% at which level the anti-resoiling benefits become particularly significant. More preferably at least 0.1wt% of polymer is present, most preferably at least 0.2%wt.
  • higher levels of polymer than 3%wt or even 2%wt do not give significant further cleaning advantages taking common 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 use, 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.
  • One or more solvents may be present in the compositions of the invention.
  • the presence of solvents is often beneficial .
  • compositions of the present invention comprise not more than 25%wt of glycol ether or alkanol solvents of the general formula:
  • Rl and R2 are independently C1-C6 alkyl or H, but 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 C1-C6 branched or straight chain alkanols, more preferably one or more of methanol , ethanol , propanols or butanols. Ethanol and iso-propanol are particularly preferred.
  • the solvent comprises at least one glycol ether solvent selected from the group comprising diethylene glycol mono-n-butyl ether (available in the marketplace as Butyl
  • Digol TM 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 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 preferably at least 5%.
  • 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.
  • 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 1 products. Although both the normal and concentrated products can be used neat it 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.
  • 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 to the antimicrobial.
  • compositions comprise a preservative.
  • a suitable preservative is PROXEL LV TM or FORMOLTM.
  • 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.
  • 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 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 repellents are the terpenoids, particularly limonene.
  • oils many are known to show antimicrobial effects as well as being insect repellents and/or perfumes and can therefore perform more than one function.
  • 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 according to the invention can contain other minor ingredients which are not essential, but aid in their cleaning performance and in maintaining the physical and chemical stability of the product .
  • the composition can contain detergent builders.
  • 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 DEQU ⁇ _E--.STTM 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 .
  • 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 and betaine at the same time is believed to be less desirable as these surfactants interact and form a complex which inhibits the synergistic hygiene activity of the amphoterics with the organic acid.
  • the formations according to the invention are free of anionic surfactants when betaine is 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 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.
  • 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 possible to make compositions which contain little or no anionic surfactant .
  • Suitable hydrotropes include, alkali metal toluene sulphonates, urea, alkali metal xylene and cumene 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 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 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°C. The cumene sulphonate is the most preferred hydrotrope.
  • ethoxylated nonionic levels of around 7%wt 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%.
  • 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 C8-C24 fatty acids, and preferably C10-C20. Particularly useful are the sodium and potassium and mono-, di- and tri-ethanolamine salts of the mixtures of fatty acids derived from coconut oil and ground nut oil. When employed, the amount of soap can form at least 0.005%, preferably 0.5% - 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 in these condensation products 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
  • m is 1-5.
  • a particularly preferred material has C9-C11, 5-8EO, 1- 3P0, most preferably C9-C11, 6E0, 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.
  • 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 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 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.
  • compositions according to the present invention have a pH of 3-8 and comprise:
  • 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 least one of acrylic acid, methacrylic acid, maleic anhydride, ethylene, styrene and methyl vinyl ether,
  • a UVA-B absorbing material preferably a benzophenone derivative
  • compositions A and B are set out as compositions A and B below.
  • compositions can also be manufactured which are essentially dry powders and which form the compositions of the invention on addition of water.
  • compositions according to the invention were compared with products which were available in the Brazilian market.
  • a typical heavy duty cleaners in this market is
  • Veja TM available from Reckitt & Colman.
  • a further known product is "Domex TM and is manufactured by Lever.
  • the Domex product was formulated as follows
  • the order of addition is important, since the UV absorbing material is difficult to dissolve in water.
  • a pre-mixture of the UV absorber in solvent is prepared and the remaining components are admixed before the UV absorber/solvent is added.
  • a pre-mixture of UV absorber/Butyl Digol at 10% concentration 0.5 g UV absorber in 5 g Butyl Digol was added after all the other components to give a final product concentration of 0.01-
  • UV light absorbance was measured with a spectrophotometer .
  • Table 3 shows the results.
  • compositions of the invention are both effective cleaners and effectively reduce UV exposure of surfaces which have been treated with them.

Abstract

The invention concerns hard surface cleaning compositions comprising a nonionic surfactant, a UV absorber and a water soluble anionic polymer. The compositions leave sufficient UV-absorber on the surface after cleaning to provide extended protection of the surface against the damaging effect of UV light. Preferably the compositions also contain a hydrotrope such as an aromatic sulphonate salt and/or an organic solvent such as a glycol ether or a lower aliphatic alcohol.

Description

HARD SURFACE CLEANERS
Field of the Invention
The present invention relates to hard surface cleaning compositions which contain a UV absorbing agent .
Background to the Invention
Many household fittings fixtures and furnishings suffer from the harmful effects of the suns rays. This can, for example 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 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 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:
a) a non-reactive UVA compound
b) an emulsifying or dispersing agent for the UVA compound c) water d) optionally, a polysiloxane based product.
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 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 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 compositions which contain UV absorbing agents.
Brief Description of the Invention
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 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: 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, wherein, the ratio of polymer : nonionic is 0.1:1 or less, and
c) 0.01-5wt% of a UV-absorbing agent,
(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 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 cleaned.
Detailed Description of the Invention
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) . 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 methoxycinnamic acid esters such as octyl methoxycinnamate 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, 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 .
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%.
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 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 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 .
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. Surfactants :
It is essential that the compositions of the present invention comprise at least one nonionic surfactant component, preferably in an amount of l-30%wt. Of the nonionic surfactants alkoxylated alcohols, alkoxylated 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 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 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 ™ (ex HENKEL)
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 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. Ethoxylated aliphatic alcohols are 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 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 .
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 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 CIO alcohols with 5-8 moles of ethylene oxide .
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 .
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 solubilisation of the polymer at high pH's as mentioned above. Typically the cationic surfactants are quaternary ammonium salts of the general formula RιR2R3R4N 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 monovalent anion equivalent .
The cationic surfactants are preferably the quaternary nitrogen compounds wherein 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 . Preferably X is a halogen, most preferably chloride or bromide.
Preferably Rl 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 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 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 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-dimethyl -ammonium chloride (available in the marketplace as BARDAC 2250) , 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.
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 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 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, 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 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 "secondary1 cleaning effort.
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 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 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 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.
Polymers :
As noted above the polymers according to the invention are water soluble polymers having an average molecular weight of 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 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 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, 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.
Preferably, the average molecular weight of the polymer is at least 5000, more preferably at least 50,000 and most
TM preferably in excess of 100,000. VERSICOL E-ll (ex. Allied 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 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.
Preferably the level of polymer is 0.05-4.0wt% at which level 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 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 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 polymer is reduced.
Solvents :
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 invention comprise not more than 25%wt of glycol ether or alkanol solvents of the general formula:
Rl-0-(E0)m-(PO)n-R2,
wherein Rl and R2 are independently C1-C6 alkyl or H, but 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 C1-C6 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 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 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 preferably at least 5%.
Antimicrobials :
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.
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, 'concentrated1 products. Although both the normal and concentrated products can be used neat it 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.
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 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 TM or FORMOL™.
Insect Repellent Materials:
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. 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 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 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 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.
Minors and Optional Components :
The compositions according to the invention can contain other 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. 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 DEQU ■_E--.STTM 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 .
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 and betaine at the same time is believed to be less desirable 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 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 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 possible to make compositions which contain little or no anionic surfactant .
Suitable hydrotropes include, alkali metal toluene sulphonates, urea, alkali metal xylene and cumene 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 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 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°C. The cumene sulphonate is the most preferred hydrotrope. For ethoxylated nonionic levels of around 7%wt 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%.
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 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-, 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.
Further examples of 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 in these condensation products lies in the range 1:5-5:1. Particularly preferred ethoxylated/propoxylated nonionics include molecules of the general formula :
RO(EO)n(PO)mH
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, 5-8EO, 1- 3P0, most preferably C9-C11, 6E0, 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.
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 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 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.
Preferred Composition:
Preferred compositions according to the present invention have a pH of 3-8 and comprise:
a) l-10%wt of 2-15EO ethoxylated C8-C18 alcohol nonionic surfactant,
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 least one of acrylic acid, methacrylic acid, maleic anhydride, ethylene, styrene and methyl vinyl ether,
c) 0.01-l%wt of a UVA-B absorbing material, preferably a benzophenone derivative
d) less than l%wt of anionic surfactants, and,
e) 0.1-4%wt of a hydrotrope
Alternative preferred compositions are set out as compositions A and B below.
Figure imgf000020_0001
Compositions can also be manufactured which are essentially dry powders and which form the compositions of the invention on addition of water.
In order that the present invention may be further understood it will be described hereinafter by way of example :
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 market. A typical heavy duty cleaners in this market is
Veja TM, available from Reckitt & Colman. A further known product is "Domex TM and is manufactured by Lever.
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 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:
Table 1
Figure imgf000021_0001
Figure imgf000022_0001
The Domex product was formulated as follows
Table 2
Figure imgf000022_0002
In the above exemplary formulation the order of addition is important, since the UV absorbing material is difficult to 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 absorber in 5 g Butyl Digol) was added after all the other components to give a final product concentration of 0.01-
UV light absorbance was measured with a spectrophotometer . Table 3 shows the results.
Table 3
Figure imgf000023_0001
The measurements in Table 3 clearly show the effectiveness 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 can be seen that the comparative product (comp) which did not contain the absorbing material had little or no UV adsorbance .
Example 2 : cleaning performance :
In order to demonstrate that the products according to the 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
Formica TM or enamel which had been soiled in a standard manner . Table 4
Figure imgf000024_0001
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 been treated with them.

Claims

1. A hard surface cleaning composition comprising:
a) 0.1-50%wt nonionic surfactant,
b) 0.005-5%wt of a water soluble, anionic polymer having an average molecular weight of less than
1,000,000, wherein the ratio of polymer : nonionic is 0.1:1 or less and,
c) 0.01-5wt% of a UV-absorbing agent
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 either together or with other monomers.
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 aforementioned with ethylene, styrene and methyl vinyl ether .
4. Composition according to claims 1-3 which further comprises 0.005-5%wt of a cationic surfactant.
Composition according to claims 1-4 having a pH of 3-12. Composition according to claim 1-5 which further comprises a glycol ether or alkanol solvent of the general formula:
Rl-0- (E0)m- (PO)n-R2,
wherein Rl and R2 are independently Cl-6 alkyl or H, but not both hydrogen, m and n are independently 0-5
Composition according to claims 1-6 wherein the UV absorbing agent comprises a benzophenone derivative.
8. Composition according to claim 7 which comprises 2-hydroxy-4-methoxybenzophenone.
9. Composition according to claim 7 which comprises phenylbenzimidazole sulphonic acid.
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.
PCT/EP1999/000246 1998-01-19 1999-01-08 Hard surface cleaners WO1999036499A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2000540204A JP2002509186A (en) 1998-01-19 1999-01-08 Hard surface cleaner
HU0100524A HUP0100524A3 (en) 1998-01-19 1999-01-08 Hard surface cleaner composition and a method for reducing uv damage
AU32495/99A AU3249599A (en) 1998-01-19 1999-01-08 Hard surface cleaners
CA002317544A CA2317544A1 (en) 1998-01-19 1999-01-08 Hard surface cleaners
EP99930894A EP1049762A1 (en) 1998-01-19 1999-01-08 Hard surface cleaners

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9801078.8A GB9801078D0 (en) 1998-01-19 1998-01-19 Improvements relating to hard surface cleaners
GB9801078.8 1998-01-19

Publications (1)

Publication Number Publication Date
WO1999036499A1 true WO1999036499A1 (en) 1999-07-22

Family

ID=10825507

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/000246 WO1999036499A1 (en) 1998-01-19 1999-01-08 Hard surface cleaners

Country Status (13)

Country Link
EP (1) EP1049762A1 (en)
JP (1) JP2002509186A (en)
AR (1) AR014414A1 (en)
AU (1) AU3249599A (en)
BR (1) BR9900073A (en)
CA (1) CA2317544A1 (en)
GB (1) GB9801078D0 (en)
HU (1) HUP0100524A3 (en)
ID (1) ID25481A (en)
TR (1) TR200002087T2 (en)
UY (1) UY25362A1 (en)
WO (1) WO1999036499A1 (en)
ZA (1) ZA99188B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001004251A1 (en) * 1999-07-12 2001-01-18 Unilever N.V. Hard surface cleaning composition comprising a uva-filter
WO2001030955A1 (en) * 1999-10-22 2001-05-03 The Procter & Gamble Company Compositions for treating shoes and methods and articles employing same
WO2001038470A1 (en) * 1999-11-25 2001-05-31 Unilever Plc Method of treating fabric
JP2003510411A (en) * 1999-09-23 2003-03-18 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン Liquid multiphase cleaning composition
EP1403360A1 (en) * 2002-09-27 2004-03-31 Unilever N.V. Cleaning composition and wipe
US6861396B2 (en) 2000-10-20 2005-03-01 The Procter & Gamble Company Compositions for pre-treating shoes and methods and articles employing same
WO2011020733A3 (en) * 2009-08-19 2011-06-03 Unilever Nv Device to clean substrates
WO2011020731A3 (en) * 2009-08-19 2011-06-03 Unilever Nv A process for cleaning hard surfaces
US8800089B2 (en) 2009-08-19 2014-08-12 Conopco, Inc. Process for cleaning teeth
US10280385B2 (en) 2015-03-05 2019-05-07 Nicca Chemical Co., Ltd. Detergent composition for hard surfaces

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2010001832A (en) * 2007-09-05 2010-03-11 Basf Se Home and fabric care compositions comprising dye-polymer complexes.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4333385A1 (en) * 1993-09-30 1995-04-06 Friedrich A Spruegel Surface disinfectant and cleaning agent
WO1996011249A1 (en) * 1994-10-05 1996-04-18 S.C. Johnson & Son, Inc. Cleaning composition
WO1997006232A1 (en) * 1995-08-07 1997-02-20 Unilever Plc Improvements relating to hard surface cleaning composition
WO1997044422A1 (en) * 1996-05-23 1997-11-27 Unilever Plc Detergent composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4333385A1 (en) * 1993-09-30 1995-04-06 Friedrich A Spruegel Surface disinfectant and cleaning agent
WO1996011249A1 (en) * 1994-10-05 1996-04-18 S.C. Johnson & Son, Inc. Cleaning composition
WO1997006232A1 (en) * 1995-08-07 1997-02-20 Unilever Plc Improvements relating to hard surface cleaning composition
WO1997044422A1 (en) * 1996-05-23 1997-11-27 Unilever Plc Detergent composition

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001004251A1 (en) * 1999-07-12 2001-01-18 Unilever N.V. Hard surface cleaning composition comprising a uva-filter
JP2003510411A (en) * 1999-09-23 2003-03-18 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチエン Liquid multiphase cleaning composition
WO2001030955A1 (en) * 1999-10-22 2001-05-03 The Procter & Gamble Company Compositions for treating shoes and methods and articles employing same
US6750188B2 (en) 1999-10-22 2004-06-15 The Procter & Gamble Company Compositions for treating shoes and methods and articles employing same
US6866888B2 (en) 1999-10-22 2005-03-15 The Procter & Gamble Company Compositions for treating shoes and methods and articles employing same
WO2001038470A1 (en) * 1999-11-25 2001-05-31 Unilever Plc Method of treating fabric
US6861396B2 (en) 2000-10-20 2005-03-01 The Procter & Gamble Company Compositions for pre-treating shoes and methods and articles employing same
EP1403360A1 (en) * 2002-09-27 2004-03-31 Unilever N.V. Cleaning composition and wipe
WO2011020733A3 (en) * 2009-08-19 2011-06-03 Unilever Nv Device to clean substrates
WO2011020731A3 (en) * 2009-08-19 2011-06-03 Unilever Nv A process for cleaning hard surfaces
CN102548671A (en) * 2009-08-19 2012-07-04 荷兰联合利华有限公司 A process for cleaning hard surfaces
US8685174B2 (en) 2009-08-19 2014-04-01 Conopco, Inc. Process for cleaning hard surfaces
US8800089B2 (en) 2009-08-19 2014-08-12 Conopco, Inc. Process for cleaning teeth
US8910889B2 (en) 2009-08-19 2014-12-16 Conopco, Inc. Process and a device to clean substrates
EA021348B1 (en) * 2009-08-19 2015-05-29 Юнилевер Н.В. A process for cleaning an article such as fabric article
EA021742B1 (en) * 2009-08-19 2015-08-31 Юнилевер Н.В. A process for cleaning hard surfaces
CN102548671B (en) * 2009-08-19 2016-01-20 荷兰联合利华有限公司 The method of cleaning of hard surfaces
US10280385B2 (en) 2015-03-05 2019-05-07 Nicca Chemical Co., Ltd. Detergent composition for hard surfaces

Also Published As

Publication number Publication date
ID25481A (en) 2000-10-05
AR014414A1 (en) 2001-02-28
TR200002087T2 (en) 2000-12-21
HUP0100524A2 (en) 2001-06-28
GB9801078D0 (en) 1998-03-18
UY25362A1 (en) 1999-09-27
EP1049762A1 (en) 2000-11-08
ZA99188B (en) 2000-07-12
CA2317544A1 (en) 1999-07-22
BR9900073A (en) 2000-01-11
HUP0100524A3 (en) 2002-02-28
AU3249599A (en) 1999-08-02
JP2002509186A (en) 2002-03-26

Similar Documents

Publication Publication Date Title
AU689354B2 (en) Improvements relating to antimicrobial cleaning compositions
US6268330B1 (en) Clear microemulsion acidic light duty liquid cleaning compositions
DE60030544T2 (en) LIQUID ALL-PURPOSE CLEANER FOR BATHROOM
US10696930B2 (en) Solvent containing anitmicrobial hard surface cleaning compositions
CA2215156C (en) Perfumed compositions comprising polymer and nonionic surfactant
CA2158541C (en) Cleaning compositions with short chain nonionic surfactants
WO1999036499A1 (en) Hard surface cleaners
AU780889B2 (en) Acidic light duty liquid cleaning compositions
WO1998012294A1 (en) Antimicrobial cleaning compositions
BR112020017802A2 (en) WATER CLEANING FORMULATION
EP0748865B1 (en) Stable liquid cleaners containing pine oil
WO1997043369A1 (en) Insect-repellent compositions comprising antimicrobial agents and nonionic surfactant
CZ169999A3 (en) Spray liquid disinfecting preparation, packaging process thereof and disinfection of surfaces
AU2012325190B2 (en) Cleansing composition
WO2018237129A1 (en) Solvent containing hard surface cleaning compositions
WO1999036501A1 (en) Process for preparing detergent compositions
US5981455A (en) Cleaning compositions with short chain nonionic surfactants
WO1999036500A1 (en) Hard surface cleaners
WO2001004251A1 (en) Hard surface cleaning composition comprising a uva-filter
CN111819273B (en) Aqueous light duty liquid detergent formulations
US6746999B1 (en) Light duty liquid cleaning compositions consisting of anionic surfactant mixtures
CZ97499A3 (en) Cleansing agent
CZ170099A3 (en) Spraying liquid disinfecting preparation, packaging method thereof and disinfecting of surfaces
CA2826961A1 (en) Alkaline cleaning compositions

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1999930894

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 32495/99

Country of ref document: AU

ENP Entry into the national phase

Ref document number: 2317544

Country of ref document: CA

Ref document number: 2317544

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2000/02087

Country of ref document: TR

NENP Non-entry into the national phase

Ref country code: KR

WWP Wipo information: published in national office

Ref document number: 1999930894

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 1999930894

Country of ref document: EP