EP1456335A1 - Hard surface treatment method and compositions and polymeric materials for use therein - Google Patents

Hard surface treatment method and compositions and polymeric materials for use therein

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Publication number
EP1456335A1
EP1456335A1 EP02790439A EP02790439A EP1456335A1 EP 1456335 A1 EP1456335 A1 EP 1456335A1 EP 02790439 A EP02790439 A EP 02790439A EP 02790439 A EP02790439 A EP 02790439A EP 1456335 A1 EP1456335 A1 EP 1456335A1
Authority
EP
European Patent Office
Prior art keywords
terminal
carboxylic acid
group
compositions according
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02790439A
Other languages
German (de)
French (fr)
Inventor
A.T. c/oUnilever R & D Port Sunlight ASHCROFT
M. c/oUnilever R & D Port Sunlight CARVELL
P. H. c/oUnilever R & D Port Sunlight FINDLAY
S.P. c/oUnilever R & D Port Sunlight RANNARD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP02790439A priority Critical patent/EP1456335A1/en
Publication of EP1456335A1 publication Critical patent/EP1456335A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

  • the present invention relates to the use of highly branched polymeric material in a method of hard surface treatment and to hard surface treatment compositions comprising such branched polymeric material.
  • the invention also relates to branched polymeric material suitable for use in the method.
  • Limescale is an important soil in bathrooms and kitchens and one that is not easy to remove. Domestic water supplies contain varying levels of calcium and magnesium salts, particularly carbonates. Residues of water left after, for instance, bathing, showering, dishwashing, rinsing etc. will be left on hard surfaces and will eventually evaporate. As it evaporates, the remaining water becomes super-saturated with respect to the salts it contains and these begin to precipitate as what is known as limescale. This scale can become progressively thicker, harder and more difficult to remove. In so-called hard water areas where calcium levels are high, tough scale deposits can form very quickly.
  • Hard surface cleaning compositions including soil release polymers have been proposed. Also, certain polymers have been disclosed to reduce heterogeneous nucleation of calcium salt crystals in water droplets drying out on a hard surface, as has been described in WO01/42415, particularly for cationic polymers .
  • a hard surface treatment composition can be used to deposit polymeric materials with a very high degree of branching onto a hard surface, which polymeric materials can affect the way in which calcium salts deposit on the surface as they form in droplets of water remaining on the hard surface, making the subsequent removal of the calcium salts easier.
  • dentritic or hyper-branched polymeric materials have been found to be suitable for deposition onto hard surfaces and thus affect the crystallinity of calcium salts as they form.
  • the present invention provides a method of treatment of hard surfaces comprising applying to the hard surface a polymeric material with a very high degree of branching, to deposit the polymeric material onto the hard surface so that the polymeric material modifies the deposition of calcium salt crystals formed in a solution of calcium salts in contact with the hard surface.
  • the invention also provides the use of such polymers in the method of treatment of hard surfaces to so modify the deposition of calcium salt crystals.
  • the present invention provides polymeric materials obtained by amidation polymerisation of at least one monomer comprising at least one terminal group of formula -NR ⁇ R 2 , at least one terminal carboxylic acid derivative, and at least one additional terminal group selected from -NR ⁇ R 2 and a carboxylic acid derivative, wherein Ri and R 2 , which may be the same or different, are groups capable of reacting with the carboxylic acid derivative.
  • This polymeric material is suitable for use in the method of the invention.
  • the present invention provides hard surface treatment compositions comprising a polymer with a very high degree of branching.
  • Figure 1 shows a schematic polymerisation sequence for the third class of polymers suitable for use in the invention.
  • Figure 2 shows a schematic reaction scheme for producing a starting material for manufacturing the fourth class of polymeric material suitable for use in the invention.
  • Figure 3 shows a schematic reaction sequence for a production of the fourth class of polymeric material suitable for use in the invention.
  • Figure 4 shows suitable starting materials for the production of the fourth class of polymeric material suitable for use in the invention, or precursors therefor.
  • ⁇ hard surface' used herein denotes the kind of surfaces in regular contact with water such as are found in kitchens, bathrooms and similar places including equipment such as taps, showers etc., used in those environments.
  • the hard surfaces are for example made of metal (e.g. aluminium or steel or chromium) , ceramic, enamel, glass or polymeric material such as polyacrylate, including filled polymeric materials.
  • the method of hard surface treatment comprises applying to the hard surface a liquid hard surface treatment composition which comprises, dissolved, emulsified or suspended therein, the polymeric material with the very high degree of branching.
  • the hard surface treatment composition may be applied in the form of concentrate, a dilute solution or it may be applied with water to dilute it in situ.
  • the method according to the invention may be preceded by a cleaning treatment of the surface, such that the polymeric material is applied to a clean surface.
  • the method may comprise cleaning as well as applying the polymer to the surface in one operation.
  • compositions are liquid and include solutions, dispersions or emulsions of the polymeric material in a liquid carrier.
  • This carrier may be water or an organic solvent or a mixture of both.
  • the carrier liquid is water or a mixture of water and a water-miscible organic solvent.
  • Particularly suitable solvents are C 1 -C 4 alcohols are mono- and di-ethylene and -propylene glycol monoalkyl ethers wherein the alkyl group has 1-6 C-atoms .
  • the compositions may be used only to deposit the polymeric material on the surface, or they may have additional functions, particularly as a cleaning composition. The latter case the compositions generally contain one or more detergent surfactants.
  • compositions may be applied by any suitable means.
  • they can be applied using an implement such as a cloth or wipe or they can be poured onto the surface directly from a container or sprayed from an aerosol can or using a spray gun applicator.
  • compositions for use in the present invention may include other ingredients useful for hard surface cleaning compositions .
  • Nominally calcium salts have a cubic morphology which allows them to bond strongly to hard surfaces, making them difficult to remove. Without wishing to be bound by theory, it is believed that altering the morphology of the crystals can reduce the contact area and bond strength between crystals and the hard surfaces, making the calcium salts easier to remove.
  • the vaterite polymorph is softer and more water soluble than calcite and is easier to remove . It has been found that certain polymers with a very high degree of branching i.e. dendritic or hyperbranched polymeric materials can interfere with the crystallisation process resulting in limescale deposits which are easier to remove .
  • the degree of branching is represented by the branching factor which is defined as 2D/2D+L wherein D is the number of monomers introducing a branching point and L is the number of monomers introducing a linear segment (see J.M.J. Freschet and C.J. Hawker: Comprehensive Polymer Science, Second Supplement p. 71, 1996, Pergamon Press, Oxford)
  • the branching factor of polymers used in the present invention is at least 0.20, preferably at least 0.35, more preferably at least 0.49.
  • the branching factor may be measured by spectroscopic techniques for example proton or carbon NMR spectroscopy.
  • dendritic or hyperbranched polymeric materials comprise a large number of amine and/or amide groups in the polymeric chain. Even more suitable are such polymers in which tertiary amine nitrogen occupies the branching points in the polymer structure.
  • a group of suitable dendritic or hyperbranched polymers may be obtained by polymerisation sequences involving Michael addition of amine groups to ethylenically unsaturated monomers comprising a carboxylic acid derivative, such as a cyano, amide, ester, acid chloride or anhydride group.
  • a carboxylic acid derivative such as a cyano, amide, ester, acid chloride or anhydride group.
  • Particularly suitable polymerisation sequences and polymers obtained thereby are described below in classes one to three
  • Class one of dendritic or hyperbranched polymers suitable for use in the present invention are manufactured by the following steps:
  • a diamine monomer is reacted by Michael addition with an ethylenically unsaturated cyanide compound, preferably acrylonitrile, to yield compounds having three or four (preferably four) terminal cyanide groups.
  • an ethylenically unsaturated cyanide compound preferably acrylonitrile
  • the cyanide groups are reduced, for example with hydrogen in the presence of a transition metal (e.g. platinum) catalyst, to yield compounds having three or four terminal primary amine groups .
  • a transition metal e.g. platinum
  • reaction product is then subjected to successive reduction of the cyanide groups followed by Michael addition of ethylenically unsaturated cyanide to the amines thus formed.
  • the resulting polymeric material comprises a dendritic polymer that is branched at most or even substantially every nitrogen atom.
  • Suitable dendritic polymers of this type for use in the present invention can be manufactured from 1,4-diamino- butane and acrylonitrile and have a weight average molecular weight in the region of 1,000 - 16,000
  • Class two of polymers suitable for use in the present invention are manufactured by the following steps:
  • This compound is then subjected to amidation with a compound having at least two primary amine groups, for example 1, 2-diaminoethane, to yield a compound having two or three terminal primary amine groups.
  • a compound having at least two primary amine groups for example 1, 2-diaminoethane
  • reaction product is then subjected to successive Michael additions with ethylenically unsaturated carboxylic acid derivative and amidation reactions with a diamine to produce a dendritic polymer.
  • Polymers particularly suitable for use in the invention are manufactured from ammonia and methyl acrylate and have a weight average molecular weight in the region of 1,000 to 900,000.
  • Class three of polymers that are suitable for use in the present invention are manufactured from a monomer obtained from the following process: (i) A compound is taken, having two terminal -NR 1 R 2 groups, wherein R] . and R 2 may be the same or different and are each capable of reacting with a carboxylic acid derivative. Ri and R 2 are suitably each hydrogen.
  • One of the terminal RR 2 groups is protected with a suitable protecting group.
  • the other group is then reacted with a compound having an ethylenic unsaturation (preferably terminal) and a terminal reactive carboxylic acid derivative capable of, for example an ethylenically unsaturated acid chloride such as acrylic acid chloride, to yield a compound having a protected NR ⁇ R 2 group, an amide bond and an ethylenic unsaturation.
  • the protective group is then removed to provide a monomer comprising a terminal NR X R 2 group and a (preferably terminal) ethylenic unsaturation.
  • This monomer can be subsequently homopolymerised by Michael additions.
  • the resulting polymeric material is a mixture complex hyperbranched polymers with a distribution of masses and imperfect branching.
  • a particularly suitable monomer obtained and polymerised this way is N- (2-aminoethyl) -prop-3-enoyl amide.
  • a typical sequence of initial polymerisation reactions is shown for this molecule in Figure 1.
  • Hyperbranched polymers of this third type preferably have a weight average molecular weight in the region of 1,000 - 20,000 and branching factor greater than or equal to 0.49.
  • Another and particularly suitable group of polymers for use in the present invention is obtained by polymerising a monomer having at least one terminal - R ! R 2 group, at least one terminal carboxylic acid derivative capable of reacting with the -NRiR 2 group, for example an ester, acid chloride, or acid anhydride, and at least one further group selected from terminal -NR ⁇ R 2 groups and terminal carboxylic acid derivatives, wherein R x and R 2 may be the same on different and are such that the -NR 1 R 2 group is capable of reacting with a carboxylic acid derivative.
  • Ri and R 2 are hydrogen.
  • a monomer of this type may be obtained for example by the following sequence of reaction steps shown schematically in Figure 2 :
  • a secondary amine having two primary amine groups (preferably terminal) such as a dialkylene triamine is reacted in step one with a protecting agent to protect the terminal primary amine groups.
  • the secondary amine is then reacted in step 2 in a Michael addition with an ethylenically unsaturated carboxylic acid derivative.
  • the protecting groups are removed in step 3 to obtain a compound having two primary amine groups and one (preferably terminal) carboxylic acid derivative.
  • the reaction sequence is exemplified in Figure 2 starting from diethylene triamine and methyl acrylate.
  • This monomer may then be subjected to successive amidation reactions to provide a hyperbranched polymer.
  • a typical reaction scheme for the initial reaction steps is shown in Figure 3 in which the monomer is subjected to successive amidation reactions 4, 5 etc. to yield the complex hyperbranched polymer shown.
  • Hyperbranched polymers of this fourth type preferably have a weight average molecular weight in the region of 1,000 - 20,000 and a branching factor of at least 0.49.
  • the monomer for the fourth type of polymer is preferably obtained using secondary amines substituted with two alkyl or alkenyl chains of the same or different lengths, each terminating with a primary amine group as starting materials, such as dipropylene triamine or other starting materials illustrated in Figure 4.
  • Hard surface treatment compositions according to the present invention preferably contain 0.01-10% by weight, more preferably 0.1-1.0% by weight of the polymer.
  • Surfactants :
  • compositions according to the invention also comprise one or more detergent surfactants that are generally chosen from anionic, nonionic, amphoteric, zwitterionic and cationic surfactants.
  • Preferred surfactants are chosen from anionic, nonionic, amphoteric and zwitterionic surfactants. All surfactants must be compatible with the polymer.
  • Suitable anionic surfactants are water-soluble salts of organic sulphuric acid esters and sulphonic acids which have in the molecular structure an alkyl group containing from 8 to 22 carbon atoms.
  • anionic surfactants are water-soluble salts of: long chain (i.e. 8-22 C-atom) alcohol sulphates (hereinafter referred to as PAS) , especially those obtained by sulphating the fatty alcohols produced by reducing the glycerides of tallow or coconut oil; alkyl benzene sulphonates, such as those in which the alkyl group contains from 6 to 20 carbon atoms; secondary alkanesulphonates .
  • PAS long chain alcohol sulphates
  • alkyl glyceryl ether sulphates especially those ethers of the fatty alcohols derived from tallow and coconut oil; fatty acid monoglyceride sulphates; sulphates of the reaction product of one mole of a fatty alcohol and from 1 to 6 moles of ethylene oxide; salts of alkylphenol ethyleneoxy-ether sulphates with from 1 to 8 ethyleneoxy units per molecule and in which the alkyl groups contain from 4 to 14 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with alkali; and mixtures thereof.
  • the preferred water-soluble synthetic anionic surfactants are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of alkyl-benzenesulphonates and mixtures with olefinsulphonates and alkyl sulphates, and the fatty acid mono-glyceride sulphates.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-sulphonate, and sodium dinonyl- naphthalene- sulphonate.
  • alkyl-aromatic sulphonates such as alkylbenzenesulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthal
  • synthetic anionic surfactant is to be employed the amount present in the compositions of the invention, it will generally be at least 0.1%, preferably at least 0.5%, more preferably at least 1.0%, but not more than 20%, preferably at most 10%, more preferably at most 8%
  • Suitable nonionic surfactants can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl- aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is attached to any particular hydrophobic group can be readily adjusted to yield a water- soluble compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB, taking into account the presence of the organic solvent and possible hydrocarbon co-solvent in the composition.
  • Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensates having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80% of ethyleneoxy groups by weight and having a molecular weight of from 5,000 to 11,000.
  • Alkylglycosides which are condensation products of long chain aliphatic alcohols and saccharides
  • tertiary amine oxides of structure RRRN0 where one R is an alkyl group of 8 to 18 carbon atoms and the other R groups are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyldodecylamine oxide
  • tertiary phosphine oxides of structure RRRPO where one R is an alkyl group of 8 to 18 carbon atoms and the other R groups are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide
  • dialkyl sulphoxides of structure RRSO where one R is an alkyl group of from 10 to 18 carbon atoms and the other is methyl or ethyl, for instance methyltetradecyl sulphoxide
  • fatty acid alkylolamides alkylamides
  • the amount of nonionic surfactant to be employed in the cleaning compositions of the invention will preferably be at least 0.1%, more preferably at least 0.2%, most preferably at least 0.5%.
  • the maximum amount is suitably 15%, preferably 10% and most preferably 7%.
  • compositions may contain amounts of both anionic and nonionic surfactants which are chosen, bearing in mind the level of electrolyte present, so as to provide a structured liquid detergent composition, i.e. one which is ' self- thickened' .
  • a structured liquid detergent composition i.e. one which is ' self- thickened' .
  • the weight ratio of anionic surfactant to nonionic surfactant may vary, taking the above considerations in mind, and will depend on their nature, but is preferably in the range of from 1:9 to 9:1, more preferably from 1:4 to 4:1, and ideally above 1:1.
  • the cleaning compositions will comprise from 0 to 10% by weight of a water-soluble, synthetic anionic sulphate or sulphonate surfactant salt containing an alkyl radical having from 8 to 22 carbon atoms in the molecule, and from 0.5 to 7% by weight of an ethoxylated nonionic surfactant derived from the condensation of an aliphatic alcohol having from 8 to 22 carbon atoms in the molecule with ethylene oxide, such that the condensate has from 2 to 15 moles of ethylene oxide per mole of aliphatic alcohol.
  • Suitable amphoteric surfactants that optionally can be employed are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water- solubilising group, for instance sodium 3-dodecylamino- propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyl taurate.
  • anionic water- solubilising group for instance sodium 3-dodecylamino- propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyl taurate.
  • Suitable zwitterionic surfactants that optionally can be employed are derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance 3- (N,N-dimethyl-N-hexadecylammonium) propane-1- sulphonate betaine, 3- (dodecyl methyl sulphonium) propane-1- sulphonate betaine and 3- (cetylmethyl phosphonium) ethane sulphonate betaine .
  • surfactants are mentioned as surface-active agents in the well-known textbooks: "Surface Active Agents” Vol.l, by Schwartz & Perry, Interscience 1949; “Surface Active Agents” Vol .2 by Schwartz, Perry & Berch, Interscience 1958; the current edition of "McCutcheon* s Emulsifiers and Detergents” published by Manufacturing Confectioners Company; “Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
  • the total amount of surfactant compound to be employed will generally be from 0.1 to 20%. Preferably the amount is at least 0.5%, more preferably at least 1%. The maximum amount is usually 15% or less, preferably not more than 10%.
  • compositions according to the present invention may include abrasives such as the composition according to the invention can contain other ingredients which aid in their cleaning performance.
  • the composition can contain detergent builders such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water- soluble phosphates (especially ortho-, pyro- or polyphosphates or mixtures thereof) , zeolites and mixtures thereof in an amount of up to 25%.
  • Some of these builders can additionally function as abrasives if present in an amount in excess of their solubility in water. If present, the builder preferably will form at least 0.1% of the composition.
  • Metal ion sequestrants such as ethylenediaminetetraacetates, amino-polyphosphonates (DEQUEST ) and phosphates and a wide variety of poly-functional organic acids and salts, can also optionally be employed provided they are compatible with polymer and optional abrasive material.
  • a further optional ingredient for compositions according to the invention is a suds-regulating material, which can be employed in compositions that have a tendency to produce 5 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 and ammonium salts of fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 10 to about
  • the amount of soap can form at least 0.005%, preferably 0.1% to 2% by weight of the composition.
  • Fatty acid soaps such as Prifac 7901 have been found to be suitable for this purpose.
  • a further example of a suds-regulating material is a silicone oil or a hydrocarbon solvent.
  • compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly active chlorine or
  • peroxide compounds 25 peroxide compounds
  • gel-control agents 25 peroxide compounds
  • freeze-thaw stabilisers 25 peroxide compounds
  • bactericides 25 peroxide compounds
  • preservatives for example 1,2- benzisothiazolin-3-one
  • hydrotropes 25 peroxide compounds
  • the hard surface treatment composition can be any suitable 0 pH.
  • compositions are either mildly alkaline (particularly if they are formulated as surface cleaning compositions, in order to enhance the effect of surfactants) or neutral or slightly acidic (particularly if they include cationic species or amine groups which become protonated and cationic in an acid environment, in order to assist deposition) .
  • the compositions should not be too acidic, in order to avoid damage to acid sensitive surfaces.
  • pH is in the region 3-12, more preferred in the range 3.5-6.0 or in the range 10-12. In any event, the pH is suitably above 3.0 and more preferably above 3.5.
  • compositions used in the present invention may also include other polymeric material which reduce deposition of difficultly removable calcium and magnesium salts at hard surfaces .
  • polymeric material according to the present invention can, in addition to scale inhibiting effects, give a longer lasting shine, better surface appearance, a smooth feel to treated surfaces .
  • compositions according to the present invention are useful for treating any household surfaces in for example kitchens and bathrooms, including floors, baths, toilets, wash basins, showers, dishwashers, taps, sinks, work surfaces etc.
  • the compositions are suitably liquids. It is often desirable that such liquids are not water thin but have a more or less viscous appearance. Suitable viscosity may be obtained by a skilled combination of surfactants leading to structuring of the liquid. Alternatively, or in addition, it is possible to obtain the required viscosity using thickening compounds known in the art, such as well known thickening polymers and/or thickening clays.
  • compositions according to the invention may also be used as a component of ready-to-use wet wipes.

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Abstract

A method of hard surface treatment and liquid compositions comprising a polymeric material with a very degree of branching in a liquid carrier are described. A polymeric material obtained by polymerising a monomer having at least one terminal -NR1R2 group, at least one terminal carboxylic acid derivative capable of reacting with the -NR1R2 group and at least one further group selected from terminal NR1R2 groups and terminal carboxylic acid derivatives, wherein R1 and R2 my be the same on different and are such that the -NR1R2 group is capable of reacting with the carboxylic acid derivative.

Description

Hard surface treatment method and compositions and polymeric materials for use therein
The present invention relates to the use of highly branched polymeric material in a method of hard surface treatment and to hard surface treatment compositions comprising such branched polymeric material. The invention also relates to branched polymeric material suitable for use in the method.
Background and Prior Art
Limescale is an important soil in bathrooms and kitchens and one that is not easy to remove. Domestic water supplies contain varying levels of calcium and magnesium salts, particularly carbonates. Residues of water left after, for instance, bathing, showering, dishwashing, rinsing etc. will be left on hard surfaces and will eventually evaporate. As it evaporates, the remaining water becomes super-saturated with respect to the salts it contains and these begin to precipitate as what is known as limescale. This scale can become progressively thicker, harder and more difficult to remove. In so-called hard water areas where calcium levels are high, tough scale deposits can form very quickly.
Conventional hard surface cleaning materials intended to remove limescale contain acid in order to dissolve the deposits. However, enamel and marble surfaces are susceptible to acid damage. Abrasive may be included in hard surface cleaning compositions, but use of abrasive to remove tough scale can lead to damage to the underlying surface.
Thus far, it has not been possible to provide effective and satisfactory limescale removing compositions.
Hard surface cleaning compositions including soil release polymers have been proposed. Also, certain polymers have been disclosed to reduce heterogeneous nucleation of calcium salt crystals in water droplets drying out on a hard surface, as has been described in WO01/42415, particularly for cationic polymers .
It has been found that a hard surface treatment composition can be used to deposit polymeric materials with a very high degree of branching onto a hard surface, which polymeric materials can affect the way in which calcium salts deposit on the surface as they form in droplets of water remaining on the hard surface, making the subsequent removal of the calcium salts easier.
In particular, dentritic or hyper-branched polymeric materials have been found to be suitable for deposition onto hard surfaces and thus affect the crystallinity of calcium salts as they form.
Summary of Invention
Accordingly, the present invention provides a method of treatment of hard surfaces comprising applying to the hard surface a polymeric material with a very high degree of branching, to deposit the polymeric material onto the hard surface so that the polymeric material modifies the deposition of calcium salt crystals formed in a solution of calcium salts in contact with the hard surface. The invention also provides the use of such polymers in the method of treatment of hard surfaces to so modify the deposition of calcium salt crystals.
In another aspect, the present invention provides polymeric materials obtained by amidation polymerisation of at least one monomer comprising at least one terminal group of formula -NRχR2, at least one terminal carboxylic acid derivative, and at least one additional terminal group selected from -NRχR2 and a carboxylic acid derivative, wherein Ri and R2, which may be the same or different, are groups capable of reacting with the carboxylic acid derivative. This polymeric material is suitable for use in the method of the invention.
In a further aspect, the present invention provides hard surface treatment compositions comprising a polymer with a very high degree of branching.
Brief description of drawings
Figure 1 shows a schematic polymerisation sequence for the third class of polymers suitable for use in the invention. Figure 2 shows a schematic reaction scheme for producing a starting material for manufacturing the fourth class of polymeric material suitable for use in the invention.
Figure 3 shows a schematic reaction sequence for a production of the fourth class of polymeric material suitable for use in the invention.
Figure 4 shows suitable starting materials for the production of the fourth class of polymeric material suitable for use in the invention, or precursors therefor.
Detailed Description of the Invention
Percentages mentioned hereinbelow are by weight calculated on the total composition unless specifically mentioned otherwise .
Method of Hard Surface Treatment
The term Λhard surface' used herein denotes the kind of surfaces in regular contact with water such as are found in kitchens, bathrooms and similar places including equipment such as taps, showers etc., used in those environments. The hard surfaces are for example made of metal (e.g. aluminium or steel or chromium) , ceramic, enamel, glass or polymeric material such as polyacrylate, including filled polymeric materials.
The method of hard surface treatment comprises applying to the hard surface a liquid hard surface treatment composition which comprises, dissolved, emulsified or suspended therein, the polymeric material with the very high degree of branching. The hard surface treatment composition may be applied in the form of concentrate, a dilute solution or it may be applied with water to dilute it in situ.
The method according to the invention may be preceded by a cleaning treatment of the surface, such that the polymeric material is applied to a clean surface. Alternatively and preferably, the method may comprise cleaning as well as applying the polymer to the surface in one operation.
Hard Surface Treatment Compositions
Suitable compositions are liquid and include solutions, dispersions or emulsions of the polymeric material in a liquid carrier. This carrier may be water or an organic solvent or a mixture of both. Preferably the carrier liquid is water or a mixture of water and a water-miscible organic solvent. Particularly suitable solvents are C1-C4 alcohols are mono- and di-ethylene and -propylene glycol monoalkyl ethers wherein the alkyl group has 1-6 C-atoms . As indicated above, the compositions may be used only to deposit the polymeric material on the surface, or they may have additional functions, particularly as a cleaning composition. The latter case the compositions generally contain one or more detergent surfactants.
The compositions may be applied by any suitable means. For example, they can be applied using an implement such as a cloth or wipe or they can be poured onto the surface directly from a container or sprayed from an aerosol can or using a spray gun applicator.
Compositions for use in the present invention may include other ingredients useful for hard surface cleaning compositions .
Polymeric Material
Without wishing to be bound by theory, it is believed that, when water comprising low levels of dissolved calcium salts is left as droplets or pools on hard surfaces after domestic washing and rinsing operations, a small proportion of polymeric material present on the surface dissolves into the water. Such dissolved polymeric material can lead to modification of the shape or size of calcium salt crystals formed as the water in the droplet evaporates. In particular it can alter the crystal morphology of calcium carbonate from cubic or favour the preferred formation of a vaterite polymorph over the calcite polymorph.
Nominally calcium salts have a cubic morphology which allows them to bond strongly to hard surfaces, making them difficult to remove. Without wishing to be bound by theory, it is believed that altering the morphology of the crystals can reduce the contact area and bond strength between crystals and the hard surfaces, making the calcium salts easier to remove. The vaterite polymorph is softer and more water soluble than calcite and is easier to remove . It has been found that certain polymers with a very high degree of branching i.e. dendritic or hyperbranched polymeric materials can interfere with the crystallisation process resulting in limescale deposits which are easier to remove .
The degree of branching is represented by the branching factor which is defined as 2D/2D+L wherein D is the number of monomers introducing a branching point and L is the number of monomers introducing a linear segment (see J.M.J. Freschet and C.J. Hawker: Comprehensive Polymer Science, Second Supplement p. 71, 1996, Pergamon Press, Oxford) Preferably, the branching factor of polymers used in the present invention is at least 0.20, preferably at least 0.35, more preferably at least 0.49. The branching factor may be measured by spectroscopic techniques for example proton or carbon NMR spectroscopy.
Particularly suitable dendritic or hyperbranched polymeric materials comprise a large number of amine and/or amide groups in the polymeric chain. Even more suitable are such polymers in which tertiary amine nitrogen occupies the branching points in the polymer structure.
Accordingly, a group of suitable dendritic or hyperbranched polymers may be obtained by polymerisation sequences involving Michael addition of amine groups to ethylenically unsaturated monomers comprising a carboxylic acid derivative, such as a cyano, amide, ester, acid chloride or anhydride group. Particularly suitable polymerisation sequences and polymers obtained thereby are described below in classes one to three
Class one of dendritic or hyperbranched polymers suitable for use in the present invention are manufactured by the following steps:
(a) a diamine monomer is reacted by Michael addition with an ethylenically unsaturated cyanide compound, preferably acrylonitrile, to yield compounds having three or four (preferably four) terminal cyanide groups.
(b) the cyanide groups are reduced, for example with hydrogen in the presence of a transition metal (e.g. platinum) catalyst, to yield compounds having three or four terminal primary amine groups .
(c) the compounds thus obtained are reacted with more ethylenically unsaturated cyanide compound to yield compounds having up to 8 (preferably 8) terminal cyanide groups.
(d) the reaction product is then subjected to successive reduction of the cyanide groups followed by Michael addition of ethylenically unsaturated cyanide to the amines thus formed.
The resulting polymeric material comprises a dendritic polymer that is branched at most or even substantially every nitrogen atom. Suitable dendritic polymers of this type for use in the present invention can be manufactured from 1,4-diamino- butane and acrylonitrile and have a weight average molecular weight in the region of 1,000 - 16,000
Class two of polymers suitable for use in the present invention are manufactured by the following steps:
(i) Ammonia or a primary amine is reacted with an ethylenically unsaturated carboxylic acid derivative, for example an acrylate or methacrylate by a Michael addition to yield a compound having two or three terminal carboxylic acid derivative groups.
(ii) This compound is then subjected to amidation with a compound having at least two primary amine groups, for example 1, 2-diaminoethane, to yield a compound having two or three terminal primary amine groups.
(iii) The reaction product is then subjected to successive Michael additions with ethylenically unsaturated carboxylic acid derivative and amidation reactions with a diamine to produce a dendritic polymer.
Polymers particularly suitable for use in the invention are manufactured from ammonia and methyl acrylate and have a weight average molecular weight in the region of 1,000 to 900,000.
Class three of polymers that are suitable for use in the present invention are manufactured from a monomer obtained from the following process: (i) A compound is taken, having two terminal -NR1R2 groups, wherein R]. and R2 may be the same or different and are each capable of reacting with a carboxylic acid derivative. Ri and R2 are suitably each hydrogen.
(ii) One of the terminal RR2 groups is protected with a suitable protecting group. The other group is then reacted with a compound having an ethylenic unsaturation (preferably terminal) and a terminal reactive carboxylic acid derivative capable of, for example an ethylenically unsaturated acid chloride such as acrylic acid chloride, to yield a compound having a protected NRχR2 group, an amide bond and an ethylenic unsaturation. The protective group is then removed to provide a monomer comprising a terminal NRXR2 group and a (preferably terminal) ethylenic unsaturation.
This monomer can be subsequently homopolymerised by Michael additions. The resulting polymeric material is a mixture complex hyperbranched polymers with a distribution of masses and imperfect branching.
A particularly suitable monomer obtained and polymerised this way is N- (2-aminoethyl) -prop-3-enoyl amide. A typical sequence of initial polymerisation reactions is shown for this molecule in Figure 1. Hyperbranched polymers of this third type preferably have a weight average molecular weight in the region of 1,000 - 20,000 and branching factor greater than or equal to 0.49.
Another and particularly suitable group of polymers for use in the present invention is obtained by polymerising a monomer having at least one terminal - R!R2 group, at least one terminal carboxylic acid derivative capable of reacting with the -NRiR2 group, for example an ester, acid chloride, or acid anhydride, and at least one further group selected from terminal -NRιR2 groups and terminal carboxylic acid derivatives, wherein Rx and R2 may be the same on different and are such that the -NR1R2 group is capable of reacting with a carboxylic acid derivative. Preferably Ri and R2 are hydrogen. A suitable example of reaction sequences and the polymer obtained thereby are described as the fourth class below.
A monomer of this type may be obtained for example by the following sequence of reaction steps shown schematically in Figure 2 :
A secondary amine having two primary amine groups (preferably terminal) such as a dialkylene triamine is reacted in step one with a protecting agent to protect the terminal primary amine groups. The secondary amine is then reacted in step 2 in a Michael addition with an ethylenically unsaturated carboxylic acid derivative. The protecting groups are removed in step 3 to obtain a compound having two primary amine groups and one (preferably terminal) carboxylic acid derivative. The reaction sequence is exemplified in Figure 2 starting from diethylene triamine and methyl acrylate.
This monomer may then be subjected to successive amidation reactions to provide a hyperbranched polymer. A typical reaction scheme for the initial reaction steps is shown in Figure 3 in which the monomer is subjected to successive amidation reactions 4, 5 etc. to yield the complex hyperbranched polymer shown.
Hyperbranched polymers of this fourth type preferably have a weight average molecular weight in the region of 1,000 - 20,000 and a branching factor of at least 0.49.
The monomer for the fourth type of polymer is preferably obtained using secondary amines substituted with two alkyl or alkenyl chains of the same or different lengths, each terminating with a primary amine group as starting materials, such as dipropylene triamine or other starting materials illustrated in Figure 4.
Other suitable examples of monomers for the fourth type of polymers are also shown in Figure 4.
Hard surface treatment compositions according to the present invention preferably contain 0.01-10% by weight, more preferably 0.1-1.0% by weight of the polymer. Surfactants :
Preferred compositions according to the invention also comprise one or more detergent surfactants that are generally chosen from anionic, nonionic, amphoteric, zwitterionic and cationic surfactants. Preferred surfactants are chosen from anionic, nonionic, amphoteric and zwitterionic surfactants. All surfactants must be compatible with the polymer.
Suitable anionic surfactants are water-soluble salts of organic sulphuric acid esters and sulphonic acids which have in the molecular structure an alkyl group containing from 8 to 22 carbon atoms.
Examples of such anionic surfactants are water-soluble salts of: long chain (i.e. 8-22 C-atom) alcohol sulphates (hereinafter referred to as PAS) , especially those obtained by sulphating the fatty alcohols produced by reducing the glycerides of tallow or coconut oil; alkyl benzene sulphonates, such as those in which the alkyl group contains from 6 to 20 carbon atoms; secondary alkanesulphonates .
Also suitable are salts of:
alkyl glyceryl ether sulphates, especially those ethers of the fatty alcohols derived from tallow and coconut oil; fatty acid monoglyceride sulphates; sulphates of the reaction product of one mole of a fatty alcohol and from 1 to 6 moles of ethylene oxide; salts of alkylphenol ethyleneoxy-ether sulphates with from 1 to 8 ethyleneoxy units per molecule and in which the alkyl groups contain from 4 to 14 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with alkali; and mixtures thereof.
The preferred water-soluble synthetic anionic surfactants are the alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of alkyl-benzenesulphonates and mixtures with olefinsulphonates and alkyl sulphates, and the fatty acid mono-glyceride sulphates. The most preferred anionic surfactants are alkyl-aromatic sulphonates such as alkylbenzenesulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are sodium salts of alkylbenzenesulphonates or of alkyl-toluene-, -xylene- or -phenolsulphonates, alkylnaphthalene-sulphonates, ammonium diamylnaphthalene-sulphonate, and sodium dinonyl- naphthalene- sulphonate.
If synthetic anionic surfactant is to be employed the amount present in the compositions of the invention, it will generally be at least 0.1%, preferably at least 0.5%, more preferably at least 1.0%, but not more than 20%, preferably at most 10%, more preferably at most 8%
Suitable nonionic surfactants can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl- aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is attached to any particular hydrophobic group can be readily adjusted to yield a water- soluble compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB, taking into account the presence of the organic solvent and possible hydrocarbon co-solvent in the composition.
Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensates having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensates containing from 40 to 80% of ethyleneoxy groups by weight and having a molecular weight of from 5,000 to 11,000.
Other examples are: Alkylglycosides which are condensation products of long chain aliphatic alcohols and saccharides; tertiary amine oxides of structure RRRN0, where one R is an alkyl group of 8 to 18 carbon atoms and the other R groups are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyldodecylamine oxide; tertiary phosphine oxides of structure RRRPO, where one R is an alkyl group of 8 to 18 carbon atoms and the other R groups are each alkyl or hydroxyalkyl groups of 1 to 3 carbon atoms, for instance dimethyl-dodecylphosphine oxide; and dialkyl sulphoxides of structure RRSO where one R is an alkyl group of from 10 to 18 carbon atoms and the other is methyl or ethyl, for instance methyltetradecyl sulphoxide; fatty acid alkylolamides; alkylene oxide condensates of fatty acid alkylolamides and alkyl mercaptans . Ethoxylated aliphatic alcohols are particularly preferred.
The amount of nonionic surfactant to be employed in the cleaning compositions of the invention will preferably be at least 0.1%, more preferably at least 0.2%, most preferably at least 0.5%. The maximum amount is suitably 15%, preferably 10% and most preferably 7%.
The compositions may contain amounts of both anionic and nonionic surfactants which are chosen, bearing in mind the level of electrolyte present, so as to provide a structured liquid detergent composition, i.e. one which is ' self- thickened' . Thus, in spite of the presence of organic solvent, thickened liquid cleaning compositions can be made without the need to employ any additional thickening agent and which nevertheless have a long shelf life over a wide temperature range.
The weight ratio of anionic surfactant to nonionic surfactant may vary, taking the above considerations in mind, and will depend on their nature, but is preferably in the range of from 1:9 to 9:1, more preferably from 1:4 to 4:1, and ideally above 1:1. According to an embodiment, illustrating this aspect of the invention, the cleaning compositions will comprise from 0 to 10% by weight of a water-soluble, synthetic anionic sulphate or sulphonate surfactant salt containing an alkyl radical having from 8 to 22 carbon atoms in the molecule, and from 0.5 to 7% by weight of an ethoxylated nonionic surfactant derived from the condensation of an aliphatic alcohol having from 8 to 22 carbon atoms in the molecule with ethylene oxide, such that the condensate has from 2 to 15 moles of ethylene oxide per mole of aliphatic alcohol.
Suitable amphoteric surfactants that optionally can be employed are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water- solubilising group, for instance sodium 3-dodecylamino- propionate, sodium 3-dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyl taurate.
Suitable zwitterionic surfactants that optionally can be employed are derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic group of from 8 to 18 carbon atoms and an aliphatic group substituted by an anionic water-solubilising group, for instance 3- (N,N-dimethyl-N-hexadecylammonium) propane-1- sulphonate betaine, 3- (dodecyl methyl sulphonium) propane-1- sulphonate betaine and 3- (cetylmethyl phosphonium) ethane sulphonate betaine .
Numerous examples of suitable surfactants are mentioned as surface-active agents in the well-known textbooks: "Surface Active Agents" Vol.l, by Schwartz & Perry, Interscience 1949; "Surface Active Agents" Vol .2 by Schwartz, Perry & Berch, Interscience 1958; the current edition of "McCutcheon* s Emulsifiers and Detergents" published by Manufacturing Confectioners Company; "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.
If surfactants are to be present in the compositions of the present invention, the total amount of surfactant compound to be employed will generally be from 0.1 to 20%. Preferably the amount is at least 0.5%, more preferably at least 1%. The maximum amount is usually 15% or less, preferably not more than 10%.
The compositions according to the present invention may include abrasives such as the composition according to the invention can contain other ingredients which aid in their cleaning performance. For example, the composition can contain detergent builders such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water- soluble phosphates (especially ortho-, pyro- or polyphosphates or mixtures thereof) , zeolites and mixtures thereof in an amount of up to 25%. Some of these builders can additionally function as abrasives if present in an amount in excess of their solubility in water. If present, the builder preferably will form at least 0.1% of the composition.
Metal ion sequestrants such as ethylenediaminetetraacetates, amino-polyphosphonates (DEQUEST ) and phosphates and a wide variety of poly-functional organic acids and salts, can also optionally be employed provided they are compatible with polymer and optional abrasive material. A further optional ingredient for compositions according to the invention is a suds-regulating material, which can be employed in compositions that have a tendency to produce 5 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 and ammonium salts of fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 10 to about
1020 carbon atoms. Particularly useful are the sodium and potassium and mono-, di- and triethanolamine salts of the mixtures of fatty acids derived from coconut oil and ground nut oil . When employed, the amount of soap can form at least 0.005%, preferably 0.1% to 2% by weight of the composition.
15 Fatty acid soaps such as Prifac 7901 have been found to be suitable for this purpose.
A further example of a suds-regulating material is a silicone oil or a hydrocarbon solvent.
20 Compositions according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly active chlorine or
25 peroxide compounds), gel-control agents, freeze-thaw stabilisers, bactericides, preservatives (for example 1,2- benzisothiazolin-3-one) , and hydrotropes.
The hard surface treatment composition can be any suitable 0 pH. However, it is preferred that compositions are either mildly alkaline (particularly if they are formulated as surface cleaning compositions, in order to enhance the effect of surfactants) or neutral or slightly acidic (particularly if they include cationic species or amine groups which become protonated and cationic in an acid environment, in order to assist deposition) . However, it is preferred that the compositions should not be too acidic, in order to avoid damage to acid sensitive surfaces. In particular, it is important to minimise the content of sequestering organic acids that are particularly prone to attack surfaces such as enamel. Preferably pH is in the region 3-12, more preferred in the range 3.5-6.0 or in the range 10-12. In any event, the pH is suitably above 3.0 and more preferably above 3.5.
Compositions used in the present invention may also include other polymeric material which reduce deposition of difficultly removable calcium and magnesium salts at hard surfaces .
Use of polymeric material according to the present invention can, in addition to scale inhibiting effects, give a longer lasting shine, better surface appearance, a smooth feel to treated surfaces .
Compositions according to the present invention are useful for treating any household surfaces in for example kitchens and bathrooms, including floors, baths, toilets, wash basins, showers, dishwashers, taps, sinks, work surfaces etc. The compositions are suitably liquids. It is often desirable that such liquids are not water thin but have a more or less viscous appearance. Suitable viscosity may be obtained by a skilled combination of surfactants leading to structuring of the liquid. Alternatively, or in addition, it is possible to obtain the required viscosity using thickening compounds known in the art, such as well known thickening polymers and/or thickening clays.
The compositions according to the invention may also be used as a component of ready-to-use wet wipes.
Examples
The following are suitable hard surface treatment compositions according to the present invention
Example 1 - Bathroom Spray
Sodium lauryl ether sulphate 1EO 3.0%
LIAL in™ (Ethoxylated alcohol with 10EO) 3.0% Radimax (non sequestering acid pH regulant) 4.0%
Phosphoric acid 0.5% Prifac 7907 coco fatty acid 0.25%
Sodium hydroxide 0.34%
Proxcel GXL (preservative) 0.016%
Perfume 0.5%
Hyperbranched polymer of Example 3 0.5% Water to 100%
Example 2 - Cleaning Mousse
Dobanol 23™ (6.5EO) 2.5% 2-butoxy ethoxy ethanol 2.0%
Trisodium citrate 4.0%
Sodium hydroxide 0.015% Alkaline sodium silicate 0.2% Perfume 0.4%
Ammonium hydroxide 0.057% Propellant Hyperbranched polymer of Example 3 0.5% Water to 100%
Example 3 - Synthesis of hyperbranched Polymer
The following reaction sequence was followed to produce the protected monomer:
A) Carbonyl diimidazole (10.72g), KOH (0.05g), t- butanol (7.5g) and anhydrous toluene (200ml) were added to a 500ml three necked round bottom flask fitted with a reflux condenser, stirrer bar and nitrogen inlet. The mixture was heated to 60 °C and stirred for 3 hours. A clear solution was formed. Diethylene triamine (3.41g) was added to the clear solution and the reaction was heated for a further 2.5 hours. The reaction was allowed to cool to room temperature and concentrated under reduced pressure. The resulting product was dissolved in dichloromethane and washed 4 times with water. The washings were dried with sodium sulphate, filtered and concentrated under reduced pressure to yield compound 1 (8.05g, 80%). Compound 1 was verified using NMR and IR spectroscopy and electrospray mass spectrometry.
B) Compound 1 (2.0g), methyl acrylate (5.7g), anhydrous methanol (25ml) and sodium methoxide (O.Olg) were added to a 100ml three-necked round bottom flask. The flask was sealed under nitrogen for 7 days. The reaction was concentrated under reduced pressure to yield a viscous oil. The oil was treated further subject to high vacuum which yielded a waxy solid (1.5g, 60%). Compound 2 was verified using NMR and IR spectroscopy.
Synthesis of hyperbranched polymer
Compound 2 (lg) was added to a 50ml round bottom flask fitted with a drying tube. The solid was treated with HC1 (cone, 2 drops) resulting in effervescence. The solution was heated to 90 °C for 20 hours to give the polymer as a waxy solid. Confirmation of polymerisation was obtained from IR spectroscopy showing the formation of amide groups.

Claims

Claims
1. Liquid hard surface treatment compositions comprising a polymeric material with a very high degree of branching in a liquid carrier.
2. Compositions according to claim 1 wherein the liquid carrier is water or a mixture of water and a water- miscible organic solvent.
3. Compositions according to claims 1-2 wherein the amount of polymer is 0.01-10%.
4. Compositions according to claims 1-3 wherein the polymer is a dendritic or hyperbranched polymer comprises a large number of amine or amide groups in the polymeric chain.
5. Compositions according to claims 1-4 wherein in the polymer tertiary amine nitrogen occupies the branching points .
6. Compositions according to claims 1-5 wherein the polymer is obtained by a polymerisation sequence involving Michael addition of amine groups to ethylenically unsaturated monomers comprising a carboxylic acid derivative.
7. Compositions according to claims 1-5 wherein the polymer is obtained by polymerising a monomer having at least one terminal - R1R2 group, at least one terminal carboxylic acid derivative capable of reacting with the - RιR2 group and at least one further group selected from terminal -NR1R2 groups and terminal carboxylic acid derivatives, wherein Rx and R2 may be the same on different and are such that the -NRR2 group is capable of reacting with the carboxylic acid derivative.
8. Compositions according to claims 1-7 also comprising a detergent surfactant.
9. Compositions according to claim 8 wherein the surfactant is present in an amount of 0.1 - 20%.
10. A method of treatment of hard surfaces comprising applying to the surface a composition according to any one of claims 1-9.
11. A polymeric material obtained by polymerising a monomer having at least one terminal -NR].R2 group, at least one terminal carboxylic acid derivative capable of reacting with the -NR;LR2 group and at least one further group selected from terminal -NR!R2 groups and terminal carboxylic acid derivatives, wherein Ri and R2 may be the same on different and are such that the -NRR2 group is capable of reacting with the carboxylic acid derivative.
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