WO2014185927A1 - Composition de nettoyant - Google Patents

Composition de nettoyant Download PDF

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Publication number
WO2014185927A1
WO2014185927A1 PCT/US2013/041516 US2013041516W WO2014185927A1 WO 2014185927 A1 WO2014185927 A1 WO 2014185927A1 US 2013041516 W US2013041516 W US 2013041516W WO 2014185927 A1 WO2014185927 A1 WO 2014185927A1
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WIPO (PCT)
Prior art keywords
hard surface
surface cleaner
backbone
carbon
independently
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PCT/US2013/041516
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English (en)
Inventor
Stephen Armstrong
Thomas Charles Castle
Abraham CAZES GRYJ
Jose Manuel FERNANDEZ SANCHEZ
Melanie Jane Hughes
Maria del Carmen MADRIGAL TISCARENO
Rodrigo Alejandro MENA-BRITO SANCHEZ
David Alan Pears
Maurice PRESTON
Luis Javier RIVERA CRUZ
Pennadam Shanmugam Sivanand
Santiago Salas VENTURA
Original Assignee
Colgate-Palmolive Company
Revolymer (U.K.) Limited
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 Colgate-Palmolive Company, Revolymer (U.K.) Limited filed Critical Colgate-Palmolive Company
Priority to PCT/US2013/041516 priority Critical patent/WO2014185927A1/fr
Priority to UY0001035574A priority patent/UY35574A/es
Priority to ARP140101969A priority patent/AR096328A1/es
Publication of WO2014185927A1 publication Critical patent/WO2014185927A1/fr

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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
    • C11D3/3788—Graft polymers

Definitions

  • cleaner compositions for cleaning many types of hard surfaces.
  • the main purpose of the cleaner is to clean the surface, but it would be desirable to have additional benefits provided to the hard surface. Some of these benefits would be noticeable to a person and could provide an indication to the person that the surface is clean. Therefore, it is desirable to provide a hard surface cleaner with additional benefits.
  • a hard surface cleaner comprising an amphiphilic copolymer, wherein the amphiphilic copolymer is
  • a graft copolymer comprising a hydrophobic straight or branched chain carbon-carbon backbone having at least one hydrophilic side chain, wherein each hydrophilic side chain is independently of formula (I),
  • R 1 and R 2 are each independently H, -C(0)WR 4 or -C(0)Q;
  • R 1 and R 2 are the group -C(0)Q;
  • R 1 and R 2 together form a cyclic structure together with the carbon atoms to which they are attached, of formula (II)
  • R 3 and R 5 are each independently H or alkyl
  • W is O or NR 4 ;
  • T is a group of formula -N-Y-X 2 -P;
  • X 1 is O, S or NR 4 ;
  • X 2 is O, S, (CH 2 ) p or NR 4 ;
  • p 0 to 6;
  • each R 4 is independently H or alkyl
  • P is H or another backbone
  • Y is a hydrophilic polymeric group
  • B is a straight or branched chain polymer backbone which is a copolymer of at least one ethylenically-unsaturated hydrocarbon monomer comprising at least 2 carbon atoms and maleic anhydride, and each OR' is a hydrophilic side chain attached to the backbone, wherein x denotes the number of side chains and is in the range 1 to 5000.
  • Also provided is a method of treating a hard surface to at least one of increase gloss on the hard surface, reduce malodor on the hard surface, reduce foaming of the hard surface cleaner, or provide anti-redeposition to the hard surface comprising applying the hard surface cleaner to the hard surface and wiping the hard surface cleaner across the hard surface.
  • amphiphilic copolymer for at least one of increasing gloss on a hard surface, reducing malodor on the hard surface, reducing foaming in a hard surface cleaner when the hard surface cleaner is used to clean a hard surface, or providing anti- redeposition to the hard surface.
  • molecular weight refers to number average molecular weight.
  • copolymer refers to a polymeric system in which two or more different monomers are polymerised together.
  • amphiphilic copolymer refers to a copolymer in which there are clearly definable hydrophilic and hydrophobic portions.
  • alkyl when used for the amphiphilic copolymer encompasses a linear or branched alkyl group of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • aryl encompasses any functional group or substituent derived from an aromatic ring or a heteroaromatic ring, preferably a C6 to C20 aromatic ring, for example, phenyl, benzyl, tolyl or napthyl.
  • compositions of the present invention comprise at least one amphiphilic copolymer.
  • the composition of the present invention comprises between 1 and 4 amphiphilic copolymers, for example 1, 2, 3, or 4 copolymers, preferably one or two copolymers, most preferably one copolymer.
  • the amphiphilic copolymer may have a hydrophilic-lyphophilic (or hydrophobic) balance (HLB) as measured by Griffin's method of less than or equal to 15, preferably less than or equal to 10, more preferably between 1 and 10, yet more preferably between 2 and 9, for example, between 3 and 8.
  • HLB hydrophilic-lyphophilic balance
  • the molecular mass of the hydrophilic and hydrophobic portions of the polymer may be estimated from the quantities of the relevant monomers put in as feedstocks in the amphiphilic copolymer's manufacture and an understanding of the kinetics of the reaction.
  • the composition of the final product may be checked by comparing the relevant intensities of signals from each block or portion using 1H nuclear magnetic resonance spectroscopy.
  • any other quantitative spectroscopic technique such as infra-red spectroscopy or ultra-violet visible spectroscopy may be used to confirm the structure, provided the different portions give clearly identifiable and measurable contributions to the resulting spectra.
  • a gel permeation chromatography (GPC) may be used to measure the molecular weight of the resulting materials.
  • the amphiphilic copolymer is a graft copolymer comprising a hydrophobic straight or branched chain carbon-carbon backbone having at least one hydrophilic side chain attached thereto.
  • hydrophilic side chains of the graft copolymer are each independently of formula (I),
  • R 1 and R 2 are each independently H, -C(0)WR 4 or -C(0)Q;
  • R 1 and R 2 are the group -C(0)Q;
  • R 1 and R 2 together form a cyclic structure together with the carbon atoms to which they are attached, of formula (II)
  • R 3 and R 5 are each independently H or alkyl
  • W is O or NR 4 ;
  • T is a group of formula -N-Y-X 2 -P;
  • X 1 is O, S or NR 4 ;
  • X 2 is O, S, (CH 2 ) p or NR 4 ;
  • p 0 to 6;
  • each R 4 is independently H or alkyl
  • P is H or another backbone
  • Y is a hydrophilic polymeric group.
  • the hydrophilic polymeric group Y is a poly(alkylene oxide), polyglycidol, poly(vinyl alcohol), poly(ethylene imine), poly(styrene sulphonate) or poly(acrylic acid). More preferably, the hydrophilic polymeric group Y is a polyalkylene oxide, such as polyethylene oxide or a copolymer thereof.
  • the hydrophilic polymeric group Y is of formula - (Alk 1 -0)b-(Alk 2 -0) c -, wherein Alk 1 and Alk 2 are each independently an alkylene group having from 2 to 4 carbon atoms, and b and c are each independently an integer from 1 to 125; provided that the sum b + c has a value in the range of from 10 to 250, more preferably, from 10 to 120.
  • the graft copolymer has from 1 to 5000, preferably from 1 to 300, and more preferably from 1 to 150, pendant hydrophilic groups attached thereto.
  • the graft copolymer may have between 1 to 10, between 1 to 5, or between 2 to 8 pendant hydrophilic groups attached thereto.
  • Each side chain of the graft polymer preferably has a molecular weight from 800 to 10,000.
  • each side chain may have a molecular weight between 1000 to 7500, between 2500 to 5000 or between 6000 and 9000.
  • a graft copolymer is typically produced by the reaction of hydrophilic grafts with a reactive group at a single site on the carbon-carbon backbone, i.e. the reaction uses monofunctional grafts.
  • the reaction uses monofunctional grafts.
  • a hydrophilic graft that has two sites that will react with the carbon- carbon backbone; i.e. a difunctional hydrophilic graft that can act as a cross-linking agent is used.
  • the cross-linked or chain extended copolymers comprise a linear or branched carbon-carbon backbone and a difunctional graft or a mixture of monofunctional and difunctional grafts. More preferably, the cross-linked or chain extended copolymers comprise a carbon-carbon backbone functionalized with maleic anhydride or a derivative thereof (as described herein) and an alkylene oxide such as those described in formula (II). Most preferably, the cross-linked or chain extended copolymers comprise a carbon-carbon backbone derived from polyisoprene or polybutadiene functionalized with maleic anhydride or a derivative thereof, and further comprise hydrophilic grafts being polyethylene oxide or a copolymer thereof.
  • the carbon-carbon polymer backbone is derived from a homopolymer of an ethylenically-unsaturated polymerizable hydrocarbon monomer or from a copolymer of two or more ethylenically-unsaturated polymerizable hydrocarbon monomers.
  • the carbon-carbon polymer backbone is derived from an ethylenically- unsaturated polymerizable hydrocarbon monomer containing 4 or 5 carbon atoms.
  • the carbon-carbon polymer backbone is derived from isobutylene, 1,3-butadiene, isoprene or octadecene, or a mixture thereof.
  • the copolymer comprises a carbon-carbon backbone (e.g. polyisoprene or polybutadiene) onto which maleic anhydride or maleic anhydride acid/ester groups have been grafted.
  • the carbon-carbon backbone comprises from 1 to 50 wt % maleic anhydride group.
  • maleic anhydride (MA) group it will be possible to replace the maleic anhydride (MA) group with maleic acid and salts thereof and maleic acid ester and salts thereof and mixtures thereof. Unless otherwise noted, where maleic anhydride is referred to these groups may also usefully be used in its place in the invention to obtains substantially similar results.
  • Particularly preferred examples of polymers in which the maleic anhydride is grafted onto the polymeric backbone include oly(isoprene-gr t-maleic anhydride) (PIP-g-MA)
  • n are each independently an integer from 1 to 20000.
  • Such polymers are available commercially from for instance Kuraray (sold under the name LIR-403) and the Sigma Aldrich company.
  • a further preferred example includes polyisoprene-gr t-monoacid monomethyl ester (PIP-g-MaMme)
  • n are each independently an integer from 1 to 20000.
  • Such polymers are available commercially from for instance Kuraray (sold under the name LIR-410) and the Sigma Aldrich company.
  • Another preferred example includes poly(butadiene-gra t-maleic anhydride) (PBD-g- MA)
  • n are each independently an integer from 1 to 20000.
  • a range of polybutadiene polymers functionalised with maleic anhydride are sold under the Ricon brand by Sartomer (e.g. Ricon 130MA8) and Lithene by Synthomer (e.g. N4-5000- 5 MA).
  • the maleic anhydride group coupling chemistry provides a convenient method for attaching the grafts to the copolymer backbone.
  • the skilled person would appreciate that other functional groups would be equally effective in this regard.
  • the reaction of another acyl group e.g. a suitable carboxylic acid or acyl chloride
  • a hydroxyl functionalised polymer will be suitable for forming an ester linkage between the graft and backbone.
  • Various strategies for performing coupling reactions, or click chemistry are also known in the art and may be utilised by functionalising the backbone with suitable groups, possibly in the presence of a suitable catalyst.
  • the reaction of an alkyl or aryl chloride group on the backbone with a hydroxyl group for instance (i.e. a Williamson coupling), or the reaction of a silicon hydride with an allyl group (a hydrosilyation reaction) could be utilised.
  • the carbon-carbon backbone comprises from 1 to 50 wt % maleic anhydride.
  • the backbone of the amphiphilic polymer has a molecular weight from 1,000 to 10,000.
  • the carbon-carbon backbone is a copolymer of:
  • the MA group monomer is thus present in the actual backbone rather than pendant to it.
  • a number of such materials are available commercially, most typicaly obtained by the radical polymerisation of a mixture of a maleic anhydride group and one or more other ethylenically unsaturated monomers. It will be envisioned that any number of monomers, though most typically a mixture of a maleic anhydride group and one other monomer (to make a bipolymer) or two other polymers (to make a terpolymer) will be used.
  • the maleic anhydride group monomer is maleic anhydride.
  • the other monomer is ethylene, isobutylene, 1,3-butadiene, isoprene, methyl vinyl ether, a C10-C20 terminal alkene, such as octadecene, styrene, or a mixture thereof.
  • the other monomer is isobutylene, octadecene or styrene.
  • the percentage of the monomers, and thus functionality in the resulting polymer, may be altered to provide optimal fit to the application.
  • One advantage of backbones prepared by such a method is that they offer the potential for higher loadings of maleic anhydride potentially available for reaction with hydroxy, amine, or sufide functionalised grafts (e.g. suitable PEOs,
  • MPEOs or amine functionalised alkyl ethxoylates like certain Jeffamines MPEOs or amine functionalised alkyl ethxoylates like certain Jeffamines.
  • the backbone is an alternating copolymer prepared by mixing and susbsequently polymerising equimolar quantities of a MA group and another monomer.
  • a particularly preffered backbone copolymer is poly(isobutylene-a/t-maleic anhydride)
  • n is between 5 and 4000, more preferably 10 and 1200.
  • This polymer is available commercialy from Sigma-Aldrich and Kuraray Co. Ltd; Kuraray supply the material under the trade name ISOBAM.
  • a further preffered backbone copolymer is poly(maleic anhydride-alt- 1-octadecene) (C18-alt-MA) (available from the Chevron Philips Chemical Company LLC and Sigma Aldrich).
  • n is between 1 and 5000, more preferably 10 and 150.
  • PA18 is a solid linear polyanhydride resin derived from 1-octadecene and maleic anhydride in a 1 : 1 molar ratio.
  • a further preffered backbone copolymer is poly(styrene-a/t-maleic anhydride) (PS-alt-)
  • N is 1 to 5000, optionally 10 to 150.
  • PS-alt-MA is available from a number of suppliers including Sartomer under the SMA trade name (e.g. SMA 1000F and SMA 1000P which are said to possses a M n of 2,000 and M w of 5,500).
  • SMA 1000F and SMA 1000P which are said to possses a M n of 2,000 and M w of 5,500.
  • Variants are also available in which the molar ratio of styrene to maleic anhydride varies from 1 : 1 are also available commercially and useful in the invention.
  • SMA 2000 F and P contains a 2: 1 ratio of styrene to anhydride
  • SMA 3000 F and P contains a 3: 1 ratio of styrene to anhydride. It will be understood by those skilled in the art these may best be described as statistical or random copolymers.
  • a number of useful backbones are also manufactured by Kraton (e.g. Kraton FG) and Lyondell (e.g Plexar 1000 series) in which maleic anhydride is grafted onto polymers or copolymers of monomers such as ethylene, propylene, butylene, styrene and/or vinyl acetate.
  • Poly(ethylene-a/t-maleic anhydride) is available from a number of suppliers including Vertellus under the ZeMac trade name.
  • Poly(methyl vinyl ether-a/t-maleic anhydride) is available from International Speciality Products under the Gantrez trade name.
  • Poly(ethylene -co-butyl acrylate-co-maleic anhydride) materials can be obtained from Arkema, and are sold under the trade name of Lotader (e.g. 2210, 3210, 4210, and 3410 grades). Copolymers in which the butyl acrylate is replaced by other alkyl acrylates (including methyl acrylate [grades 3430, 4404, and 4503] and ethyl acrylate [grades 6200, 8200, 3300, TX 8030, 7500, 5500, 4700, and 4720) are also available and also sold in the Lotader range. A number of the Orevac materials (grades 9309, 9314, 9307 Y, 9318, 9304, 9305) are suitable ethylene-vinyl acetate-maleic anhydride terpolymers.
  • suitable side chains precursors are those discussed below, such as mono methoxy poly(ethylene oxide) (MPEO), poly(vinyl alcohol) and poly(acrylic acid). These may for instance be purchased from the Sigma-Aldrich company. Suitable polyethylene imines are available from BASF under the Lupasol trade name.
  • amphiphilic copolymer is prepared by reacting a compound of formula (III
  • R 3 and R 5 are each independently H or alkyl, and R 6 and R 7 are each independently H or an acyl group, provided that at least one of R 6 and R 7 is an acyl group, or R 6 and R 7 are linked to form, together with the carbon atoms to which they are attached, a group of formula (V),
  • n and m are each independently an integer from 1 to 20 000.
  • m is 1 to 1000, more preferably 1 to 100 and yet more preferably 10 to 50.
  • n is 1 to 5000, more preferably 5 to 2000 and yet more preferably 10 to 1000.
  • m is 1 to 100 and n is 5 to 2000;
  • X 1 is O, S or NR 4 ;
  • X 2 is O, S, (CH 2 ) p or NR 4 ;
  • p 0 to 6;
  • each R 4 is independently H or alkyl
  • P is H or another backbone
  • Y is a hydrophilic polymeric group.
  • amphiphilic copolymer is prepared by reacting a compound of formula (Ilia),
  • n and m are as defined above, with a side chain precursor of formula (VI) as defined above.
  • the side chain precursor is of formula (Via)
  • X 1 is O or NH and X 2 is (CH 2 ) P and o is an integer from 5 to 250, preferably 10 to 100.
  • the side chain precursor is of formula (VIb)
  • R is H or alkyl
  • X 1 is O or NH
  • X 2 is (CH 2 ) P and the sum of a and b is an integer from 5 to 600, preferably 10 to 100.
  • the copolymer is prepared by grafting a monofunctional hydrophilic polymer such as poly(ethylene glycol)/poly(ethylene oxide) onto the maleic anhydride residues on the carbon-carbon backbone to form an amphiphilic copolymer of formula (VII),
  • each of m and n is independently an integer from 1 to 20 000.
  • m is 1 to 1000, more preferably 1 to 100 and yet more preferably 10 to 50.
  • n is 1 to 5000, more preferably 5 to 2000 and yet more preferably 10 to 1000.
  • m is 1 to 100 and n is 5 to 2000.
  • o is an integer from 5 to 600, preferably 10 to 100.
  • the above example shows an alcohol functionalized PEO reacting with the maleic anhydride on a PIP-g-MA backbone.
  • Suitable PIP-g-MA backbones are commercially available (for example, LIR-403 grade from Kuraray, which has approximately 3.5 MA units per chain).
  • the copolymer is prepared by adding a ratio of 2:8 equivalents of MPEG with respect to each maleic anhydride (MA) group. This essentially enables complete conversion of the maleic anhydride groups into the PEG functionalized esters.
  • the copolymer is prepared by adding a 1 : 1 ratio of methoxy poly(ethylene oxide) (MPEO) to maleic anhydride .
  • MPEO methoxy poly(ethylene oxide)
  • PEO poly(ethylene oxide) methyl ether
  • PEO poly(ethylene glycol) methyl ether
  • amphiphilic copolymer is prepared by reacting a polymer precursor of formula (Illb),
  • n and m are as defined above, with a side chain precursor of formula (VI) as defined above.
  • amphiphilic copolymer is prepared by reacting a polymer precursor of formula (IIIc),
  • n and m are as defined above, with a side chain precursor of formula (VI) as defined above.
  • the copolymer is derived from -SH or nitrogen based (NH 2 or NHR) moieties.
  • the copolymer comprises an NH 2 functionalized material.
  • the amphiphilic copolymer is prepared from a side chain precursor of formula (Vic)
  • R is H or alkyl, more preferably H or Me, and the sum of a and b is an integer from 5 to 250, preferably 10 to 100.
  • amphiphilic copolymer is of formulae (Villa) or (VHIb) and is prepared by the following reaction:
  • each of m and n is independently an integer from 1 to 20 000.
  • m is 1 to 1000, more preferably 1 to 100 and yet more preferably 10 to 50.
  • n is 1 to 5000, more preferably 5 to 2000 and yet more preferably 10 to 1000.
  • m is 1 to 100 and n is 5 to 2000.
  • o is an integer from 5 to 600, preferably 10 to 100.
  • the NH 2 functionalized material depicted above comprises two grafts on each MA, which is not possible with MPEO. This is due to the greater reactivity of the NH 2 groups compared with OH. In addition to grafting two chains per maleic anhydride unit, the greater reactivity of the NH 2 units with respect to OH leads to a product containing very small quantities of free graft.
  • the compounds of formula (III) may be replaced by compounds of formulae (IX) and (X):
  • n' is 5 to 4000 and R 3 , R 5 , R 6 and R 7 are as previously defined.
  • n' is as defined for compounds of formulae (IX) and (X).
  • the hydrophilic groups grafted onto the maleic anhydride groups are polymers of ethylene oxide (i.e. PEOs) copolymerised with propylene oxide.
  • PEOs polymers of ethylene oxide copolymerised with propylene oxide.
  • the amount of propylene oxide is preferably between 1 and 95 mol percent of the copolymer, more preferably between 2 to 50 mol percent of the copolymer, and most preferably between 5 to 30 mol percent of the copolymer.
  • the side chain precursor is of formula
  • x is 5 to 500, more preferably 10 to 100 and y is independently 1 to 125, more preferably 3 to 30.
  • x + y 6 to 600, more preferably 13 to 130.
  • the distribution of ethylene and propylene oxide units may be in the form of blocks as depicted above or as a statistical mixture. In any case the molar ratio of ethylene oxide to propylene oxide in the copolymer will favour ethylene oxide.
  • Such side chain precursors are sold commercially by Huntsman under the Jeff amine name.
  • the amphiphilic copolymer is prepared from a mixture of PIP-g-MA (polyisoprene with grafted maleic anhydride) together with MPEO (methoxy poly(ethylene oxide) and/or PEO poly(ethylene oxide).
  • MPEO methoxy poly(ethylene oxide) and/or PEO poly(ethylene oxide).
  • the MPEO and PEO have a molecular weight of 2000.
  • the amphiphilic copolymer is prepared from a mixture of PIP-g-MaMme (polyisoprene with grafted maleic monoacid monoester) together with MPEO (methoxy poly(ethylene oxide)) and/or PEO (poly(ethylene oxide)).
  • MPEO methoxy poly(ethylene oxide)
  • PEO poly(ethylene oxide)
  • the MPEO and PEO have a molecular weight of 2000.
  • amphiphilic copolymer is a graft copolymer comprising a hydrophilic straight or branched chain carbon-carbon backbone having at least one hydrophobic side chain attached thereto.
  • the hydrophilic straight or branched chain carbon-carbon backbone is a poly(alkylene oxide) or copolymer thereof, such as poly(ethylene oxide), or a copolymer thereof.
  • the hydrophobic side chain is a hydrocarbon polymer, i.e. a side chain containing only carbon and hydrogen atoms.
  • the hydrophobic side chain is derived from a homopolymer of an ethylenically-unsaturated polymerizable hydrocarbon monomer or from a copolymer of two or more ethylenically-unsaturated polymerizable hydrocarbon monomers.
  • the hydrophobic side chain may be derived from an ethylenically unsaturated hydrocarbon monomer having from 2 to 30 carbon atoms, preferably having from 3 to 20 carbon atoms, even more preferably having from 4 to 10 carbon atoms, most preferably having 4 or 5 carbon atoms, or a mixture thereof.
  • the hydrophobic side chain may be derived from ethylene, propylene, isobutylene, butadiene (1,3-butadiene), isoprene, a C10-C20 terminal alkene, such as octadecene, styrene, or a mixture thereof.
  • the hydrophobic side chain is polyisoprene, polybutadiene or a copolymer thereof.
  • the graft copolymer has from 1 to 5000, preferably from 1 to 300, and more preferably from 1 to 150, pendant hydrophobic groups attached thereto.
  • the graft copolymer may have between 1 to 10, between 1 to 5, or between 2 to 8 pendant hydrophobic groups attached thereto.
  • each side chain of the graft polymer preferably has a molecular weight from 800 to 10,000.
  • each side chain may have a molecular weight between 1000 to 7500, between 2500 to 5000 or between 6000 and 9000.
  • Each side chain of the graft polymer preferably has a molecular weight from 800 to 10,000.
  • each side chain may have a molecular weight between 1000 to 7500, between 2500 to 5000 or between 6000 and 9000.
  • hydrophobic side chains may be attached to the hydrophilic backbone using the same methods of attachment employed to attach hydrophilic side chains to a hydrophobic backbone as described above.
  • a graft copolymer is typically produced by the reaction of hydrophobic grafts with a single reactive site on the carbon-carbon backbone, i.e. the reaction uses monofunctional grafts.
  • the reaction uses monofunctional grafts.
  • a hydrophobic graft that has two sites that will react with the carbon-carbon backbone; i.e. a difunctional hydrophobic graft that can act as a cross-linking agent is used.
  • the cross-linked or chain extended copolymers comprise a linear or branched carbon-carbon backbone and a difunctional graft or a mixture of monofunctional and difunctional grafts. More preferably, the cross-linked or chain extended copolymers comprise a carbon-carbon backbone which is poly(ethylene oxide), or a copolymer thereof functionalized with maleic anhydride or a derivative thereof, and further comprise hydrophobic grafts being polyisoprene, polybutadiene or a copolymer thereof.
  • the copolymer comprises a carbon-carbon backbone, e.g. poly(ethylene oxide, onto which maleic anhydride or maleic anhydride acid/ester groups have been grafted.
  • the carbon-carbon backbone comprises from 1 to 50 wt % maleic anhydride group.
  • maleic anhydride (MA) group encompasses maleic anhydride, maleic acid and salts thereof and maleic acid ester and salts thereof and mixtures thereof.
  • the copolymer may be prepared from a poly(ethylene oxide) backbone having maleic anhydride, acid or a salt or ester thereof grafts by reacting said backbone with an OH, NH2, NHR, or SH functionalized hydrophobic side chain.
  • the maleic anhydride group coupling chemistry provides a convenient method for attaching the grafts to the copolymer backbone.
  • the skilled person would appreciate that other functional groups would be equally effective in this regard.
  • the reaction of another acyl group e.g. a suitable carboxylic acid or acyl chloride
  • a hydroxyl functionalised polymer will be suitable for forming an ester linkage between the graft and backbone.
  • acyl group e.g. a suitable carboxylic acid or acyl chloride
  • Various strategies for performing coupling reactions, or click chemistry are also known in the art and may be utilised by functionalising the backbone with suitable groups, possibly in the presence of a suitable catalyst.
  • an alkyl or aryl chloride group on the backbone with a hydroxyl group for instance (i.e. a Williamson coupling), or the reaction of a silicon hydride with an allyl group (a hydrosilyation reaction) could be utilised.
  • the carbon-carbon backbone comprises from 1 to 50 wt % maleic anhydride.
  • the backbone of the amphiphilic polymer has a molecular weight from 1,000 to 10,000.
  • the backbone is an alternating copolymer prepared by mixing and susbsequently polymerising equimolar quantities of a MA group and another monomer.
  • the copolymers used in certain embodiments are synthesised by dissolving the backbone and graft in an organic solvent (e.g. toluene) and maintaining the mixture at reflux for a period of time sufficient to ensure reaction.
  • an organic solvent e.g. toluene
  • the synthesis is carried out in the absence of solvent, i.e. using a no-solvent approach using any mixing apparatus capable of mixing the (still viscous) molten MPEO/PEO side chain and backbone together.
  • the reaction temperature is from 160 to 180 °C.
  • the reactions are preferably carried out under an inert gas to avoid oxidation of the polymers and hydrolysis of the maleic acid/anhydride groups.
  • the synthesis involves reacting from 1 to 4, more preferably, 3 equivalents of side chain precursors with respect to each acylating group. Further details of the synthesis are described in WO 09/068569 which is hereby incorporated by reference.
  • the acylating group is derived from a maleic anhydride unit (either pendant to the backbone or within the backbone).
  • Suitable side chain precursors which are poly ether amines are available commercially; a range of mono and difunctionalised amine polymers of ethylene oxide (EO) and propylene oxide (PO) are sold under the Jeffamine brand name by Huntsman. Reaction between the amine functionalized polymers with maleic anhydride derived units, for instance, can generate any of the following structures:
  • the structure denoted C may be formed by an intramolecular reaction of A, accompanied by the elimination of H 2 0. This reaction is more likely to occur with the assistance of catalysis (e.g. by the addition of an acid).
  • Both mono and difunctional amine polymers are suitable for use in the present invention.
  • hydrophilic difunctional amine side chain precursors can lead to a cross-linked or chain extended amphiphilic polymeric material.
  • mono and difunctional side chain precursors may be combined to modify the properties of the resulting polymeric material as required.
  • M-1000 and M-2070 are particularly preferred.
  • amphiphilic copolymer is prepared from the reaction of backbone precursors with a monoester of maleic anhydride, for example, to form PIP- g-MaMme (polyisoprene-graft-monoacid monomethyl ester supplied by Kuraray Co. Ltd, sold as LIR-410) with the general formula shown below:
  • PIP-g-MaMme has a functionality (i.e. n) of approximately 10, an average molecular weight of 25,000, and a glass transition temperature of -59 °C. Each monomethyl ester may react with a single amine functionality.
  • the properties of the amphiphilic copolymer depend not only on the character of the side chains grafted onto the carbon-carbon backbone, but also on the number of grafted side chains.
  • one or more chain precursors react with each backbone precursor. More preferably, a plurality of side chain precursors react with each backbone precursor.
  • the term "plurality" is defined herein as meaning more than one grafted side chain, i.e. more than one side chain precursor reacts with each backbone precursor.
  • the ratio of side chains to backbone repeat units in the resultant polymeric material is in the range of from 1 :350 to 1 :20, more preferably from 1 : 150 to 1 :30.
  • the side chains are preferably statistically distributed along the carbon-carbon backbone as the location of attachment of the side chain on the backbone will depend on the positions of suitable attachment locations in the backbone of the hydrocarbon polymer used in the manufacture.
  • each maleic anhydride unit in the polymer backbone may be derivatised with either zero, one or two side chains.
  • the side chain precursors of general formula (I) or (II) comprise at least one nucleophilic group which is an amine.
  • the nucleophilic groups react with pendant units on the polymer backbone which are acylating groups to form a polymeric material as defined above.
  • the pendant units are derived from maleic anhydride.
  • each side chain precursor has two nucleophilic groups (for instance, X 1 is O or NR 4 ) which may react with two acylating groups on different backbone precursor molecules, thereby forming a cross-linked structure.
  • X 1 is O or NR 4
  • a polyethylene oxide side chain is generally terminated with an alcohol at each end before derivatisation.
  • Each alcohol may be grafted onto a maleic anhydride unit.
  • the acylating group is derived from maleic anhydride
  • only one side chain precursor reacts per maleic anhydride monomer. This leaves the unit derived from maleic anhydride with a free carboxylic acid group, which may be derivatised at a later stage in the method. This group may also be deprotonated to give an ionic pendant group in the polymeric material.
  • the reaction between the backbone precursors (for instance, PIP-g-MA) and the side chain precursors may be carried out in an organic solvent such as toluene.
  • an organic solvent such as toluene.
  • the reaction takes place at elevated temperatures, optionally in the presence of an activator for example, triethylamine.
  • the yield may be increased by removal of the water from the reaction mixture by azeotropic distillation as toluene and water form azeotropic mixtures which boil at a lower temperature than any of the individual components.
  • the side chain precursor may also be reacted with a monoester derivative of PIP-g-MA, for example, the PIP-g-MaMme detailed above.
  • the reaction of this monomethyl ester with the side chain precursor is typically carried out in an organic solvent such as toluene at elevated temperatures. Again, the yield of ester may be increased by removing water from the reaction mixture by azeotropic distillation.
  • the synthesis of the amphiphilic copolymer may be achieved by mixing the intended side chain precursors with the backbone precursors in the absence of solvent.
  • This 'no- solvent' process eliminates the costs associated with purchasing and handling organic solvents and removing otherwise harmful materials from the polymer. It will be appreciated that this approach is also desirable in eliminating volatile organic compounds that may be harmful to the environment. Further details of the no-solvent synthesis may be found in WO 09/050203, the contents of which are hereby incorporated by reference.
  • the side chain and backbone precursors may be either in the form of a solid or in fluid form (e.g. in the form of a liquid or a gel), provided that they can be mixed easily. More preferably, the side chain and backbone precursors are either in the form of a liquid or finely ground solid. In one embodiment, the side chain precursors are in liquid form and the backbone precursors are in the form of a finely ground solid. More preferably, both the side chain and backbone precursors are in the form of a liquid at the temperature at which the acylation reaction takes place.
  • the backbone precursors are mixed with the side chain precursors by dissolving the backbone precursors in molten side chain precursors.
  • reaction process may be performed using any apparatus that is capable of providing sufficient mixing.
  • This includes reactors or other any vessels where agitation is provided, for example, by an overhead stirrer or a magnetic stirrer. More preferably, mixing is achieved using an appropriate extruder, z-blade mixer, batch mixer, U trough mixer, RT mixer, compounder, internal mixer, Banbury type mixer, two roll mill, Brabender type mixer, a wide blade mixer (or hydrofoil blade mixer), horizontal (delta or helical) blade mixer, kneader-reactor, or a variation thereof, such as a double z-blade mixer or twin screw extruder.
  • the temperature of the reaction is preferably from 50 °C to 300 °C, more preferably from 100 to 250 °C, even more preferably from 120 °C to 200 °C, and more preferably still, from 140 °C to 180 °C.
  • the mixing apparatus is flushed with an inert gas to prevent degradation of the polymeric materials.
  • the reactor may be placed under vacuum in order to ensure that air is excluded.
  • the reaction can also be catalysed by the addition of acid or base.
  • water may be added to the reactor at the end of the reaction to hydro lyse any unreacted acylating groups.
  • the hydrolysis of unreacted acylating groups can increase the hydrophilicity, and thus water compatibility or solubility, of the materials.
  • Any remaining acylating groups are preferably converted into acid groups by the addition of water to the material, or by an ageing process.
  • An ageing process typically involves leaving the material in atmospheric air to ensure hydrolysis of any residual maleic anhydride by atmospheric moisture.
  • the remaining acylating groups are hydrolysed with the aid of a base catalyst, or by the addition of an alcohol (hydroxyl) or amine with or without base.
  • any remaining maleic anhydride groups are preferably converted into diacid groups by addition of water to the material.
  • the reaction mixture at the end of the reaction, normally comprises unreacted starting materials which may include free side chain precursor and backbone precursor. There may also be some residual catalyst, if this has been used in the reaction.
  • the reaction generally produces no by-products.
  • the amphiphilic polymeric material need not be purified from the reaction mixture, since it can be advantageous to have free side chain precursors in the final composition.
  • the free side chain precursor may interact with the amphiphilic polymeric material, thereby improving its properties.
  • PIP-g-MA of appropriate molecular weight distribution and maleic anhydride content will be suitable for the synthesis of the polymeric material.
  • carboxylated PIP-g-MA materials in which the maleic anhydride is ring-opened to form a diacid or mono- acid/mono-methyl ester are also be suitable.
  • the backbone precursors of the polymeric materials are derived from polyisoprene to which maleic anhydride has been grafted.
  • the level of grafting of MA is typically around 1.0 mol % in the PIP-g-MA. In PIP-g-MaMme, the level was 2.7 mol % of the mono-acid mono-methyl ester of MA.
  • the level of grafting depends on the degree of functionalisation of the polyisoprene, the chemical functionality on the maleic anhydride and the reactivity of the graft. Only potential site for grafting is present in PIP-g- MaMme whereas two are present in MA.
  • RC11 see below
  • the number of grafts per chain when a polyether amine like Jeffamine is used is generally between 1 and 14, whereas in RC10 (see below) it is between 1 and 10.
  • An excess of graft may optionally be used.
  • preferably from 1 to 4, more preferably from 2 to 3 equivalents of side chain precursors with respect to each maleic anhydride group are reacted. Reaction efficiency is greater with the polyether amines used to synthesize RC7 as opposed to the alcohol functionalised polyether used to make RC6.
  • the molecular weight of the graft can have an effect on the degree of grafting with the 5000 molecular weight MPEO used to make RC5 reacting less efficiently than lower molecular weight graft like 1000 molecular weight MPEO used in RC 1.
  • a range of useful graft are available commercially; for instance a range of mono and difunctionalised amine polymers of ethylene oxide (EO) and propylene oxide (PO) are sold under the Jeffamine brand name by Huntsman. PEO and PEO of various molecular weights are available from Clariant and Geo Specialities.
  • the backbone precursor of the amphiphilic polymeric material is a copolymer of maleic anhydride together with an ethylenically-unsaturated monomer
  • side chain precursors are typically terminated by an alcohol or amine nucleophilic group at one end and an alkyloxy group at the other.
  • MeO-PEO-OH MPEO
  • MPEO MeO-PEO-OH
  • the reaction of maleic anhydride with an alcohol is an alcoholysis reaction which results in the formation of an ester and a carboxylic acid.
  • the reaction is also known as esterification.
  • the reaction is relatively fast and requires no catalyst, although acid or base catalysts may be used.
  • the net reaction may be represented as shown below.
  • P x and ⁇ represent the remainder of the copolymer/terpolymer and ROH is a representative side chain precursor.
  • two side chains precursors represented by ROH may react at the same maleic anhydride monomer to give a compound of general formula
  • the side chain precursors may have hydroxyl or amine groups at each of their termini and each terminus reacts with a unit derived from maleic anhydride in different backbones to form a cross-linked polymeric material.
  • any unreacted units derived from maleic anhydride in the backbone may be ring-opened. This may be performed by hydrolysis, or using a base. The resulting product may be ionisable. This further reaction step has particular utility when there is a large proportion of maleic anhydride in the backbone, for instance in an alternating copolymer.
  • the backbone precursors comprise pendant units of general formula (IV),
  • R 3 and R 5 are each independently H or alkyl, and R 6 and R 7 are each independently H or an acyl group, provided that at least one of R 6 and R 7 is an acyl group, or R 6 and R 7 are linked to form, together with the carbon atoms to which they are attached, a group of formula (V),
  • X 1 is O, S or NR 4 ;
  • X 2 is O, S, (CH 2 ) p or NR 4 ;
  • each R 4 is independently H or alkyl
  • P is H or another backbone
  • Y is a hydrophilic polymeric group
  • R 1 and R 2 are each independently H, -C(0)WR 4 or -C(0)Q;
  • R 1 and R 2 are the group -C(0)Q;
  • R 1 and R 2 together form a cyclic structure together with the carbon atoms to which they are attached, of formula (II)
  • R 3 and R 5 are each independently H or alkyl
  • W is O or NR 4 ;
  • T is a group of formula -N-Y-X 2 -P;
  • X 1 is O, S or NR 4 ;
  • p 0 to 6;
  • each R 4 is independently H or alkyl
  • P is H or another backbone
  • Y is a hydrophilic polymeric group.
  • the backbone precursors are part of the backbone itself (for example when maleic anhydride is part of the backbone), i.e.:
  • the side chains in the amphiphilic polymeric material thus comprise a unit derived from the acyl group of the backbone precursors.
  • PIP polyisoprene
  • PBD polybutadiene
  • MA maleic anhydride
  • MaMme monoacid monomethyl ester
  • PIB-alt-MA Poly(isobutylene-a/t-maleic anhydride);
  • PS-alt-MA Poly(styrene-a/t-maleic anhydride);
  • C18-alt-MA Poly(maleic anhydride-a/t-1- octadecene);
  • MPEO methoxy poly(ethylene oxide);
  • graft e.g MPEO, PEO or Jeffamine
  • graft e.g MPEO, PEO or Jeffamine
  • 1.0 equivalents of MPEO 2K were added relative to each unit of MA.
  • RC4 0.3 equivalents of MPEO 5K were added to each MA unit and thus a maximum of 30% of the MA will have reacted with graft.
  • the PIP-g-MA has an average of 2-5 MA units per chain, or typically less than 2% by weight, are available for reaction with grafts.
  • the PS-alt-MA backbone is an alternating copolymer of styrene and MA, and thus by contrast has between approximately 45 and 50 weight percent of MA.
  • more MPEO is actually added to RC7 than RC 11 and the resulting polymer would be expected to have a higher HLB than RC 11 , in other words be more hydrophilic.
  • each MA may potentially act as the coupling point for two grafts
  • MaMme may act as the coupling point for a single graft.
  • amphiphilic copolymer is RC1, RC2, RC3, RC4, RC5, RC6, RC7, RC8, RC9, RC10, RC11, or a mixture thereof.
  • the amphiphilic copolymer is present in the composition in an amount of 0.01 to 10 weight % of the composition. In other embodiments, the amount is 0.01 to 9%, 0.01 to 8%, 0.01 to 7%, 0.01 to 6%, 0.01 to 5%, 0.01 to 4%, 0.01 to 3%, 0.01 to 2%, 0.01 to 1%, 0.1 to 5%, 0.1 to 4%, 0.1 to 3%, 0.1 to 2%, 0.1 to 1%, 0.5 to 5%, 0.5 to 4%, 0.5 to 3%, 0.5 to 2%, or 0.5 to 1% by weight of the composition.
  • the amphiphilic copolymer is added to the cleaner in the form of a latex.
  • the cleaner can contain any type of surfactant, such as anionic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, or cationic surfactants.
  • the amount of surfactant can any typical amount for a cleaner. In certain embodiments, the amount of surfactant is 0.01 to 30 weight %. In other embodiments, the amount of surfactant is 0.1 up to 30, up to 25, up to 20, up to 15, up to 10, up to 9, up to 8, up to 7, up to 6, or up to 5 weight %. In other embodiments, the amount of surfactant is at least 0.2, at least 0.3, at least 0.4, at least
  • the anionic surfactant may be any of the anionic surfactants known or previously used in the art of aqueous surfactant compositions. Suitable anionic surfactants include, but are not limited to, alkyl sulfates, alkyl ether, alkaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alkylamino acids, alkyl peptides, alkoyl taurates, carboxylic acids, acyl and alkyl glutamates, alkyl isethionates, and alpha-olefm sulfonates, especially their sodium, potassium, magnesium, ammonium and mono-, di- and triethanolamine salts.
  • the alkyl groups generally contain from 8 to 18 carbon atoms and may be unsaturated.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates may contain from 1 to 10 ethylene oxide or propylene oxide units per molecule, and in certain embodiments contain 1 to 3 ethylene oxide units per molecule.
  • anionic surfactants include sodium and ammonium lauryl ether sulfate (with
  • the sulfonate surfactant is a linear alkyl benzene sulfonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, that is, wherein the benzene ring is attached in large part at the 3 or higher (for example, 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1 position is correspondingly low.
  • Suitable anionic surfactants include the olefin sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates
  • anionic surfactants include, but are not limited to, sodium dioctyl sulfosuccinate [di-(2 ethylhexyl) sodium sulfosuccinate being one] and corresponding dihexyl and dioctyl esters.
  • sulfosuccinic acid ester salts are esters of aliphatic alcohols such as saturated alkanols of 4 to 12 carbon atoms and are normally diesters of such alkanols.
  • alkali metal salts of the diesters of alcohols of 6 to 10 carbons atoms are utilized and in further embodiments, the diesters will be from octanol, such as 2-ethyl hexanol, and the sulfonic acid salt will be the sodium salt.
  • Paraffin sulfonates containing, in various embodiments, 10 to 20 or 13 to 17 carbon atoms can be used.
  • Primary paraffin sulfonates may be made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate group distributed along the paraffin chain.
  • the anionic surfactant can also include fatty acid salts (soap). Typical fatty acids are the CI 2, C14, CI 6, and CI 8 fatty acids.
  • the counter ion for the salt can be any typical counter ion, such as sodium, potassium, or magnesium.
  • the amount of anionic surfactant is 0.01 to 30 weight %. In other embodiments, the amount of anionic surfactant is 0.1 up to 30, up to 25, up to 20, up to 15, up to 10, up to 9, up to 8, up to 7, up to 6, or up to 5 weight %. In other embodiments, the amount is 0.5 to 10% or 1 to 8%.
  • the cleaner may include nonionic surfactants.
  • the nonionic surfactants may include aliphatic ethoxylated nonionic surfactants, for example, those that are commercially well known and include the primary aliphatic alcohol ethoxylates and secondary aliphatic alcohol ethoxylates.
  • the length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
  • Suitable nonionic surfactants include but are not limited to aliphatic (C6-C 18 ) primary or secondary linear or branched chain acids, alcohols or phenols, alkyl ethoxylates, alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), block alkylene oxide condensate of alkyl phenols, alkylene oxide condensates of alkanols, ethylene oxide/propylene oxide block copolymers, mono or dialkyl alkanolamides and alkyl polysaccharides, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol esters, polyoxyethylene acids, and polyoxyethylene alcohols.
  • C6-C 18 primary or secondary linear or branched chain acids
  • alcohols or phenols alkyl ethoxylates
  • alkyl phenol alkoxylates especially ethoxylates and mixed ethoxy
  • nonionic surfactants include coco mono or diethanolamide, coco diglucoside, alkyl polyglucoside, cocamidopropyl and lauramine oxide, polysorbate 20, ethoxylated linear alcohols, cetearyl alcohol, lanolin alcohol, stearic acid, glyceryl stearate, PEG- 100 stearate, and oleth 20.
  • the nonionic surfactant class also may include the condensation products of a higher alcohol (e.g., an alkanol containing 8 to 16 carbon atoms in a straight or branched chain configuration) condensed with 4 to 20 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with 16 moles of ethylene oxide (EO), tridecanol condensed with 6 to 15 moles of EO, myristyl alcohol condensed with 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to 14 carbon atoms in length and wherein the condensate contains either 6 moles of EO per mole of total alcohol or 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 1 1 EO per mole of alcohol.
  • a higher alcohol e.g., an alkan
  • nonionic surfactants include, but are not limited to, the Neodol® or Dobanol® ethoxylates (Shell Co.), which are higher aliphatic, primary alcohol containing 9 to 15 carbon atoms, such as Cg-Cn alkanol condensed with 4 to 10 moles of ethylene oxide (Neodol 91-8®, Dobanol 91-8®, Neodol 91-5®) or 2.5 moles of ethylene oxide (Neodol 91-2.5® or Dobanol 91-2.5®, C i2-Ci3 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5®), C 12- C 15 alkanol condensed with 12 moles ethylene oxide (Neodol 25- 12®), Ci4_Ci5 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13®), and the like
  • ethoxamers have an HLB (hydrophobic lipophilic balance) value of 8 to 15 and give good O/W emulsification, whereas ethoxamers with HLB values below 7 contain less than 4 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
  • HLB hydrophobic lipophilic balance
  • ethoxamers with HLB values below 7 contain less than 4 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
  • the trade names "Neodol” and “Dobanol” can be used interchangeably to refer to the same compounds, with the respective trade names used according to the geographies in which they are available.
  • Additional water soluble alcohol ethylene oxide condensates include, but are not limited to, the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • nonionic detergents of the foregoing type include Cn-C 15 secondary alkanol condensed with either 9 EO (Tergitol 15-S-9 ® ) or 12 EO (Tergitol 15-S-12 ® ) marketed by Union Carbide (USA).
  • Water soluble nonionic surfactants which can be included in the cleaner, include aliphatic ethoxylated/propoxylated nonionic surfactants, such as those depicted by the formulas:
  • R is a branched chain alkyl group having 10 to 16 carbon atoms, or an isotridecyl group and x and y are independently numbered from 0 to 20.
  • the nonionic surfactant can be present in an amount of 0.01 to 30%. In other words,
  • the amount of amine oxide is 0.1 up to 10, up to 9, up to 8, up to 7, up to 6, up to 5, up to 4, up to 3, up to 2, or up to 1 weight %. In other embodiments, the amount is at least 0.2, at least 0.3, at least 0.4, at least 0.5, or at least 1 up to 10 weight %.
  • the cleaner can include amphoteric and/or zwitterionic surfactants.
  • Amphoteric and zwitterionic surfactants are those compounds that have the capacity of behaving either as an acid or a base. Suitable zwitterionic or amphoteric surfactants include, but are not limited to, alkyl betaines, alkyl amidopropyl betaines, alkyl sulphobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphopropionates, alkyl amidopropyl
  • hydroxysultaines acyl taurates and acyl glutamates wherein the alkyl and acyl groups have about 8 to about 18 carbon atoms.
  • Examples include cocamidopropyl betaine, sodium
  • cocoamphoacetate cocoamphoacetate, cocamidopropyl hydroxysultaine, and sodium cocamphopropionate.
  • suitable zwitterionic surfactants for use herein contain both a cationic hydrophilic group (i.e., a quaternary ammonium group) and anionic hydrophilic group on the same molecule at a relatively wide range of pH's.
  • a cationic hydrophilic group i.e., a quaternary ammonium group
  • anionic hydrophilic group on the same molecule at a relatively wide range of pH's.
  • the typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
  • the zwitterionic surfactants also include hydrophobic groups including aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted
  • hydrocarbon chains that can contain linking groups such as amido groups, ester groups.
  • the hydrophobic group is an alkyl group containing about 1 to about 24 carbon atoms, in another embodiment about 8 to about 18, and in another embodiment about 10 to about 16.
  • simple alkyl groups are utilized for cost and stability reasons.
  • alkyldimethyl betaines include, but are not limited, cocodimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-dimethyl- ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine.
  • amidobetaines include cocoamidoethylbetame, cocoamido-propyl betaine or C 10 -C 14 fatty acylamidopropylene(hydropropylene)-sulfobetaine.
  • betaine is Lauryl-imino-dipropionate or Laurylamido propylbetaine.
  • the amphoteric/zwitterionic surfactant can be present in an amount of 0.01 to 30%.
  • the amount of amine oxide is 0.1 up to 10, up to 9, up to 8, up to 7, up to 6, up to 5, up to 4, up to 3, up to 2, or up to 1 weight %.
  • the amount is at least 0.2, at least 0.3, at least 0.4, at least 0.5, or at least 1 up to 10 weight %.
  • the cleaner can include an amine oxide.
  • the amine oxides are semi-polar nonionic surfactants, which include compounds and mixtures of compounds having the formula:
  • Ri is an alkyl, 2-hydroxyalkyl, 3 -hydroxy alkyl, or 3-alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, contain from 8 to 18 carbon atoms
  • R 2 and R 3 are each independently methyl, ethyl, propyl, isopropyl, 2-hydroxy ethyl, 2-hydroxypropyl, or 3- hydroxypropyl (R 2 and R 3 may be the same or different); and n is 0 to 10.
  • the cleaner can include an amine oxide of the formula: R 9
  • R 8 is a C 12-16 alkyl group or amido radical:
  • the amine oxide may be, for example, a lauryol amine oxide, a cocoamido propyl amine oxide, a cocoamido propyl dimethyl amine oxide, a lauryl/myristil amidopropyl diethylamine oxide, a lauryl/myristyl amido propyl amine oxide or a mixture of any of the foregoing.
  • the amine oxide is present in an amount of 0.01 to 30%. In other embodiments, the amount of amine oxide is 0.1 up to 10, up to 9, up to 8, up to 7, up to 6, up to 5, up to 4, up to 3, up to 2, or up to 1 weight %. In other embodiments, the amount is at least 0.2, at least 0.3, at least 0.4, at least 0.5, or at least 1 up to 10 weight %.
  • the cleaner can include cationic surfactants.
  • cationic surfactants include, but are not limited to, alkyl amines, alkyl imidazolines, ethoxylated amines, quaternary compounds, and quaternized esters.
  • alkyl amine oxides can behave as a cationic surfactant at a low pH. Examples include lauramine oxide, dicetyldimonium chloride, and cetrimonium chloride.
  • the cationic surfactant is hydroxyethyl laurdimonium chloride, which is available from Clarient as Praepagen HYTM cationic surfactant.
  • the cationic surfactant is present in an amount of 0.01 to 30%.
  • the amount of amine oxide is 0.1 up to 10, up to 9, up to 8, up to 7, up to 6, up to 5, up to 4, up to 3, up to 2, or up to 1 weight %.
  • the amount is at least 0.2, at least 0.3, at least 0.4, at least 0.5, or at least 1 up to 10 weight %. In one embodiment, the amount is 0.4 to 1.6 weight %.
  • the cleaner when a cationic surfactant is included in the cleaner, then the cleaner also includes anionic and nonionic surfactants.
  • the cleaner can include a natural gum.
  • examples of gums include, but are not limited to, xanthan gum gum, acacia, carrageenan, gelatin, guar gum, hydroxypropyl guar, karaya gum, kelp, locust bean gum, pectin, tragacanth gum, and wellan.
  • the natural gum is xanthan gum.
  • the inclusion of a natural gum in combination with polymer increases the gloss on the surface after cleaning.
  • the amount of the natural gum, such as xantham gum is 0.01 to 2 weight %. In other embodiments, the amount is 0.1 to 2, 0.1 to 1, or 0.1 to 0.5 weight %. In one embodiment, the amount is 0.1 to 0.4 weight %.
  • the cleaner can include aqueous soluble, miscible or immiscible solvents.
  • Solvents can include aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, alcohols, ether compounds, and other similar low molecular weight generally volatile liquid materials. These materials can be used in solution or as a miscible mixture or as a dispersion of the solvent in the aqueous liquid.
  • a solvent or cosolvent can be used to enhance certain soil removal properties.
  • Cosolvents include alcohols and the mono and di-alkyl ethers of alkylene glycols, dialkylene glycols, trialkylene glycols, etc. Alcohols that are useful as cosolvents include methanol, ethanol, propanol and isopropanol.
  • Representative examples of this class of cosolvent include methyl cellosolves, butyl carbitol, dibutyl carbitol, diglyme, triglyme, etc.
  • Nonaqueous liquid solvents can be used for varying compositions. These include the higher glycols, polyglycols, polyoxides and glycol ethers.
  • Suitable substances include glycol solvents (including glycol ethers or glycol acetates) such as, for example, propylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether (PM), dipropylene glycol methyl ether (DPM), propylene glycol methyl ether acetate (PMA), dipropylene glycol methyl ether acetate (CPMA), propylene glycol n-butyl ether, dipropylene glycol monobutyl ether, ethylene glycol n-butyl ether and ethylene glycol n-propyl ether, and combinations thereof.
  • the glycol solvent is propylene glycol n-butyl ether.
  • the glycol solvent is dipropylene glycol monobutyl ether.
  • Other useful solvents include ethylene oxide/propylene oxide, liquid random copolymer such as Synalox solvent series from Dow Chemical (e.g., Synalox 50-50B); propylene glycol ethers such as PnB, DPnB and TPnB (propylene glycol mono n-butyl ether, dipropylene glycol and tripropylene glycol mono n-butyl ethers sold by Dow Chemical under the trade name DowanolTM); and tripropylene glycol mono methyl ether "Dowanol TPM®" from Dow Chemical.
  • Synalox solvent series e.g., Synalox 50-50B
  • PnB, DPnB and TPnB propylene glycol mono n-butyl ether, dipropylene glycol and tripropylene glycol mono n-butyl ethers sold by Dow Chemical under the trade name DowanolTM
  • DowanolTM tripropylene glycol mono methyl ether
  • the amount of solvent can be any desired amount. In certain embodiments, the amount of solvent is 1 to 30 weight %.
  • Water can be present in any amount and generally forms the balance of the cleaner composition. In certain embodiments, the amount of water can be up to 99.9 weight % or 40 to 99.9 weight %.
  • the cleaner can also include other materials that can be typically found in many cleaners. Examples include, but are not limited to acids, bases, coloring agents, fragrances, antibacterial agents, preservatives, thickeners, hydrotropes, oxidizers, reducing agents, enzymes, enzyme stabilizing agents, builders, bleaches, bleach catalysts, or buffers. The amounts of these materials will be any customary amount used.
  • the pH of the cleaner can any pH.
  • the pH is 1 to 14, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 2 to 6, 2 to 5, 2 to 4, 3 to 6, 3 to 5, 3 to 4, 7 to 14, 7 to 13, 7 to 12, 7 to 1 1 , 7 to 10, 7 to 9, 8 to 13, 8 to 12, 8 to 1 1 , 8 to 10, 9 to 13, 9 to 12, 10 to 12, 10 to 12, or 1 1 to 13.
  • the cleaner can be used in any type of cleaner composition, such as a bucket dilutable cleaner (BDC), spray, or ready to use.
  • BDC bucket dilutable cleaner
  • the cleaner can be used to treat any type of hard surface. Examples include, but are not limited to, kitchens, sinks, counters, windows, appliances, floors, bathrooms, showers, or toilets.
  • the material for the hard surface can be any material. Examples include, but are not limited to, glass, ceramic, porcelain, metal, laminate, granite, synthetic counters, marble, tile, and concrete.
  • Also provided is a method of treating a hard surface to at least one of increase gloss on the hard surface, reduce malodor on the hard surface, reduce foaming of the hard surface cleaner, provide anti-redeposition to the hard surface, or to increase a level of disinfection on the hard surface comprising applying the hard surface cleaner to the hard surface and wiping the hard surface cleaner across the hard surface.
  • amphiphilic copolymer for at least one of increasing gloss on a hard surface, reducing malodor on the hard surface, reducing foaming in a hard surface cleaner when the hard surface cleaner is used to clean a hard surface, providing anti-redeposition to the hard surface, or increasing a level of disinfection to the hard surface.
  • Amphiphilic graft copolymers are manufactured using the methods described in PCT/GB2005/003176, PCT/EP2008/066257, PCT/EP2008/063879 and PCT/EP2008/066256.
  • the amount of the material is based on the as supplied amount and is listed as weight %.
  • DMF Dimethylformamide
  • THF tetrahydrofuran
  • Acetone, Cyclohexane, chloroform (CHCI3), diethyl ether, hexane, methyl ethyl ketone, sodium dodecylbenzene sulfonate (SDBS) and dioctyl sodium sulfosuccinate (DOSS) were obtained from Sigma Aldrich in technical grade and used as received.
  • Poly(isobutylene-alt-maleic anhydride) (PIB- alt-MA) of molecular weight 6000 and 60000 was obtained either from Sigma Aldrich or from Kuraray where the polymers are sold under the names ISOBAM-600 and ISOBAM-04.
  • Poly(maleic anhydride-alt- 1-octadecene) of molecular weight 20,000 - 25,000 was obtained either from Sigma Aldrich or from Chevron Phillips where it is sold under the name PA- 18 LV.
  • Poly(styrene-alt-maleic anhydride) (PS-alt-MA, SMA 1000) of molecular weight 2000 was obtained from Sartomer.
  • Lithene N4-9000-10MA Poly(butadiene-graft-maleic anhydride of Mn 9500M and having approximately 9.2 MA units per polymer chain) was obtained from Synthomer.
  • PIP-g-MA (sometimes referred to as MAGPI) was obtained by the reaction of maleic anhydride and polyisoprene as described in WO 2009/068569A1.
  • Poly(ethylene glycol) methyl ether of molecular weights 1000 Da (Polyglykol Ml 000), 2000 (Polyglykol M2000), and 5000 (Polyglykol M5000) were obtained from Clariant.
  • Jeffamine M-2070 amine functionalised copolymer of ethylene oxide and propylene oxide
  • Neodol 91-8 C9-11 alcohol ethoxylated with 8 units of ethylene oxide, Shell Chemicals, also sold as Dobanol 91-8
  • Neodol 25-7 C12-15 alcohol ethoxylated with 7 units of ethylene oxide, Shell Chemicals, also sold as Dobanol 25- 7
  • Synperonic 91-8 C9-11 alcohol ethoxylated with 8 units of ethylene oxide, Croda
  • BYK- 022 a VOC- free defoamer consisting of polysiloxanes and hydrophobic solids in polyglycol, Byk
  • Synperonic NCA 810 a defoa
  • Polymer RC2 was synthesized in the same manner as polymer RC1 using
  • Polymer RC5 was synthesized in the same manner as polymer RC4 using Poly(maleic anhydride-alt-l-octadecene) (Mn: 30,000 g mol " ⁇ , 25 g), poly(ethylene glycol) methyl ether (Mn: 5000 g mol " , 179 g) as the graft. Reaction was allowed to continue for a total of 72h.
  • Poly(maleic anhydride-alt-l-octadecene) Mn: 30,000 g mol " ⁇ , 25 g
  • poly(ethylene glycol) methyl ether Mn: 5000 g mol " , 179 g
  • Polymer RC6 was synthesized in the same manner as polymer RC4 using Poly(maleic anhydride-alt-l-octadecene) (M n : 30,000 g mol "1 , 50 g), poly(ethylene glycol) methyl ether
  • Polymer RC9 was synthesized in the same manner as polymer RC8 using poly(butadiene- graft- maleic anhydride (35 g, Lithene N4-9000-10MA) and poly( ethylene glycol) methyl ether
  • Synthesis Example 12 Reaction of poly(isoprene-graft-maleic acid monomethyl ester) with Jeffamine M-2070 polyether (Preparation of RC10 in a reaction flask polyisoprene- graft-maleic acid monomethyl ester)
  • Synthesis Example 13 Reaction of poly(isoprene-graft-maleic acid monomethyl ester) with Jeffamine M-2070 polyether (Preparation of RC10 in a reaction flask polyisoprene- graft-maleic acid monomethyl ester)
  • a sample of the batch of the backbone used to synthesize the graft copolymer was accurately weighed out -0.1 g (+/- 0.05 g) into the stoppered conical flask and dissolved in 10 g of accurately weighed out chloroform.
  • the FT-IR of the sample was collected, and the percentage transmission values measured at 1830 cm '1 and at 1790 cm -1 recorded.
  • the sample of the final graft copolymer was accurately weighed out -1.5 g (+/- 0.5 g) into the stoppered conical flask, dissolved in 10 g of accurately weighed out chloroform, and studied by FT-IR in a similar manner.
  • the concentration of maleic anhydride in each sample was then calculated using the following formula:
  • C is the concentration in the test solution (quoted in mg g '1 ).
  • the percentage conversion of maleic anhydride can then be determined by comparing the values from the backbone and graft copolymer. In general the grafting of MPEG onto the backbone is confirmed by observing changes in the region 1700-1850 cm " 1 associated with the maleic anhydride units.
  • Latex sample RLl was prepared in the following manner: Polymer RC11 (30 g) was dissolved in cyclohexane (70 g) to make a 30 weight% solution of polymer. A 5 weight % solution of DOSS was made by dissolving DOSS (5 g) in water (95 g). DOSS solution (55.65 g), BYK022 (7.5 g) and DI water (149.91 g) were added into a glass flanged reactor flask and the mixture was vigorously stirred by means of an overhead stirrer equipped with an anchor stirrer head. To this a 30% solution of RC11 in cyclohexane (86.94 g) was added slowly over the course of an hour.
  • the resulting mixture was then stirred for a further two hours.
  • the latex sample was then placed in a round bottom flask and the cyclohexane solvent removed from the sample under vacuum on a rotary evaporator.
  • the resulting latex was stable and did not phase separate.
  • RL2 was prepared using a 30 weight% solution of RC11 in chloroform; RL3 was prepared using a 30 weight% solution of RCl l in methyl ethyl ketone and RL4 (sp/ 138/ 174) was prepared using a 30 weight% solution of RCl l in acetone.
  • Latex sample RL5 was prepared in the following manner. Polymer RCl l (130 g) was dissolved in chloroform (304 g) to make a 30 weight% solution of polymer. A 5 weight% solution of DOSS was made by dissolving DOSS (14 g) in water (264 g). DOSS solution (278 g), BYK-022 (38 g) and DI water (750 g) were added into a 2 L beaker and the mixture was vigorously stirred by means of a Silverson laboratory homogeniser (8000 rpm) for 5 min to ensure uniformity. To this a 30% solution of RC11 in chloroform (435 g) was added slowly over the course of 30 min. The resulting mixture was then stirred for a further two hours at 8000 rpm. The latex sample was sparged overnight to remove residual chloroform. The resulting latex was stable and did not phase separate.
  • Latex sample RL6 was prepared in the following manner. A mixture of polymer RCl l (47 g), DOSS surfactant (5.5 g) and BYK-022 (2.7 g) was added to a flanged reactor flask equipped with an overhead stirrer with anchor head. The mixture was placed under a blanket of nitrogen and heated to 90 °C to melt the polymer. The powdered DOSS was dispersed in the polymer by agitating the mixture for 30 min, following which the resulting RC11/DOSS paste was allowed to cool and recovered from the reactor.
  • DI water (294 g), DOSS (3.0 g) and BYK-022 (3.0 g) were added to a glass reactor and the mixture was heated to 80 °C with agitation from an overhead reactor equipped with a pitch blade.
  • the polymer/surfactant paste (55 g) was transferred into a syringe that was heated to 80 °C.
  • Latex RL7 was prepared in a similar manner by adding a paste, made from RCl l polymer (70 g) and Neodol 91-8 (35 g), to BYK-022 (4 g) dissolved in 1% DOSS solution (210 g).
  • Latex sample RL8 was prepared in the following manner. A mixture of polymer RCl l (40 g), DOSS surfactant (4.0 g) and BYK-022 (2.0 g) was added to a flanged reactor flask equipped with an overhead stirrer with anchor head. The mixture was placed under a blanket of nitrogen and heated to 80 °C to melt the polymer. The powdered DOSS was dispersed in the polymer by agitating the mixture for 30 min. The hot paste was then slowly stirred and a hot solution of DOSS (3.0 g) and BYK-022 (3.0 g) in DI water (294 g) was then slowly added to the mixture.
  • Latex RL9 was prepared in a similar manner by adding 1% DOSS aqueous solution (350 g) to a paste made from RCl l polymer (141 g), SDBS (11.5 g). Portions of BYK-022 (2 x 5.3 g) were added to the latex periodically during manufacture as required to suppress foaming.
  • Latex RLIO was prepared in a similar manner by adding DI water (175 g) to a paste made from RCl l polymer (12.5 g), SDBS (5 g) at room temperature.
  • Latex RLl l was prepared in a similar manner by adding DI water (30 g) to a paste made from RCl l polymer (2 g), Neodol 25-7 (1 g) at room temperature.
  • Latex RL12 was prepared in a similar manner by adding 1% DOSS aqueous solution
  • Latex sample RL13 was prepared in the following manner. Polymer RCl l (10 g) was added to a flanged reactor flask equipped with an overhead stirrer with anchor head. The mixture was placed under a blanket of nitrogen and heated to 90 Stirring commenced and a hot solution of SDBS (25 g) in DI water (75 g) was then slowly added to the mixture over the course of about 1 h. After addition was complete the mixture was stirred overnight at elevated temperature before being allowed to cool to RT with continuous agitation. The resulting latex was stable and did not phase separate.
  • Latex RL14 was prepared in a similar manner by adding 5% aqueous DOSS solution
  • Latex RL15 was prepared in a similar manner by adding 10% aqueous Synperonic 91-
  • Latex RL16 was prepared in a similar manner by adding 10% aqueous Synperonic 91- 8 solution (605 g) to RCl l polymer (110 g) at 85 °C. After addition was complete the mixture was stirred for another 2 h before being allowed to cool to RT with continuous agitation.
  • Latex RL17 was prepared in a similar manner by adding 5% aqueous DOSS solution (83 g) to a mixture of RC11 polymer (15 g) and Synperonic NCA 810 at 85 °C. After addition was complete the mixture was stirred for another 1 h before being allowed to cool to RT with continuous agitation.
  • Latex sample RL17 was prepared in the following manner. DOSS (10.5 g) and BYK-022 (5.0 g) were added to DI water (199 g) in a flanged reactor flask equipped with an overhead stirrer with anchor head. The mixture was placed under a blanket of nitrogen and heated to 80 °C. RCl l polymer (45 g) was placed in a jacketed dropping funnel which was heated to 80 °C. The hot polymer was slowly added to the stirred surfactant solution over the course of about 1 h. After addition was complete the mixture was stirred for another 2 h at elevated temperature before being allowed to cool to RT with continuous agitation. The resulting latex was stable and did not phase separate. Formulation of the Amphiphilic Graft Copolymers into Hard Surface Cleaners
  • amphiphilic graft copolymers were formulated with a hard surface cleaning preparation (Desguard 20).
  • Surfactant Envirogem 360 was added to all the samples including controls to ensure better wetting onto the tiles.
  • Desguard 20 (3.7 g) was charged to a glass bottle equipped with a magnetic follower and stirring commenced using a magnetic stirrer.
  • Polymer RC3 (0.5 g) was added to the formulation which was stirred until homogenous.
  • EnviroGem 360 (0.5 g) was then added to the mixture which was left stirring for 10 min. After this the solution was let down with DI water (45 g) to the desired concentration.
  • Desguard 20 (3.7 g) was charged to a glass bottle equipped with a magnetic follower and stirring commenced using a magnetic stirrer.
  • Polymer latex RL5 (4.0 g) containing polymer RCl 1 was added to the formulation which was stirred until homogenous.
  • EnviroGem 360 (0.5 g) was then added to the mixture which was left stirring for 10 min. After this the solution was let down with DI water (41.8 g) to the desired concentration.
  • Desguard 20 (3.7 g) was charged to a glass bottle equipped with a magnetic follower and stirring commenced using a magnetic stirrer.
  • EnviroGem 360 (0.5 g) was then added to the formulation which was left stirring for 10 min. After this the solution was let down with DI water (45.8 g) to the desired concentration.
  • Example 5 Measurement of Gloss from Hard Surface Cleaning Formulations Materials used in testing were typically obtained from suppliers of building materials or similar and treated to make them appropriate and fair test substrates. For instance vinyl tiles intended for use as flooring were cut to a 150x150mm size, cleaned with water, degreased using ethanol, then allowed to dry prior to use.
  • Gloss values were measured using an Elcometer 407 Statistical Gloss Meter. A total of 9 separate measurements are recorded at different locations on the substrate and an average of the values is calculated by the gloss meter.
  • the tiles used are 10.2 cm x 10.2 cm (4 in x 4 in) vinyl tiles.
  • Gloss is measured using the following procedure. A tile is cleaned with ethanol. An initial gloss is measured at 9 points on the tile, and the results are averaged to provide an initial gloss. Add 1.5g of cleaner to be tested to the tile surface and spread evenly and allow to dry. Once dry, measure 9 points on the tile and average the results to provide a final gloss. The change in gloss is calculated by subtracting the initial gloss from the final gloss. Gloss is measured using a BYK-Gardner model Micro-gloss instrument at an angle of 85°. The gloss is also measured after a total of 6 treatments to measure the cumulative effect of the cleaner. [0234] Foam is measured using a SITA Foam Tester. The following conditions are used for the test: temperature is 23°C, sample size is 250 ml, stirrer speed is 1650 rpm, stirring duration is 30 seconds, and number of cycles is one. Foam height is measured initially and after 30 minutes. Example 6
  • compositions are made by mixing the listed materials. Gloss is measured as described above.
  • inventive compositions that contain the polymer have a higher gloss than the comparative cleaners. It can also be seen that after multiple applications, the gloss increases. For the compositions that also include xanthan gum, the initial gloss is higher.
  • compositions are made by mixing the listed materials. Gloss is measured as described above.
  • Formulas Comparative 3 and Inventive 3 are evaluated using the above described foam test.
  • Inventive 3 had an initial foam volume of 400 ml, and after 2 minutes, the foam volume was zero.
  • Comparative 3 had an initial foam volume of 1000 ml, and maintained 1000 ml of volume for about 6 minutes before decreasing to 200 ml after 15 minutes. After 20 minutes, Comparative 3 still had about 200 ml of foam volume.
  • the inclusion of the polymer provides for a reduction in foam. This is beneficial to a cleaner to have the foam decrease so that the surface is easier to rinse. Having more foam for a longer period of time makes rinsing more difficult.
  • Example 9
  • Comparative 1 The ability of the polymer to reduce malodor is evaluated. Comparative 1 and Inventive IB formulas are used. Comparative 1 is further modified to Comparative 1A by the addition of 0.25 weight % xanthan gum so that the only difference between the formulas is the inclusion of the RC-11 polymer. Each of the formulas are modified by adding either 0.88 weight % or 1 weight % of a fragrance to the formulas.
  • a malodor source is prepared by adding Malodor Concentrate (US General Services
  • Samples are prepared by adding 25 ⁇ of the 1% solution to #42 Whatman filter paper (4.25 cm size). Paper is placed in petri dish, and the solvent is allowed to evaporate for 5 minutes before covering the petri dish.
  • test surfaces are prepared as listed in 5.2.3.
  • a test suspension of Aspergillus niger is prepared according to 5.4.2.
  • the test is performed at a temperature of 25°C +/- 1°C. Place the test surfaces aseptically in a Petri dish and ensure that the dish is in a horizontal position. Prepare two test surfaces by adding 0.1ml of the test product solution and keep at equilibrated room temperature for 24hrs contact time. Inoculate the test product solution with 0.05 mL of the test suspension onto each test surface ensuring that the inoculum covers the test product. For water control, prepare the same as done for the test product solutions. After 30 minutes, transfer each of the surfaces to a separate container containing 10 mL of neutralization medium (D/E neutralizing broth from Difco) together with 5g of glass beads. Place the container in a horizontal shaking device.
  • D/E neutralizing broth from Difco neutralizing broth from Difco
  • Inventive 5 had a ME value greater than 5.6, and Comparative 5 had an ME value of 3.8.

Abstract

L'invention concerne un nettoyant de surface dure comprenant un copolymère amphiphile, le copolymère amphiphile étant un copolymère greffé comprenant une chaîne principale carbone-carbone hydrophobe à chaîne linéaire ou ramifiée sur laquelle est attachée au moins une chaîne latérale hydrophile. Le nettoyant de surface dure peut augmenter la brillance sur la surface dure tout en conservant de bonnes performances de nettoyage, réduire les mauvaises odeurs sur la surface dure, réduire le moussage du nettoyant de surface dure, conférer un effet d'antiredéposition à la surface dure ou augmenter un niveau de désinfection sur la surface dure.
PCT/US2013/041516 2013-05-17 2013-05-17 Composition de nettoyant WO2014185927A1 (fr)

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PCT/US2013/041516 WO2014185927A1 (fr) 2013-05-17 2013-05-17 Composition de nettoyant
UY0001035574A UY35574A (es) 2013-05-17 2014-05-16 Composición limpiadora de superficies duras
ARP140101969A AR096328A1 (es) 2013-05-17 2014-05-16 Composición de limpieza

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110337457A (zh) * 2017-02-24 2019-10-15 日本瑞翁株式会社 改性聚合物胶乳的制造方法
US20220268538A1 (en) * 2021-02-24 2022-08-25 Valvoline Licensing And Intellectual Property Llc Foaming evaporator coil cleaner
WO2023178580A1 (fr) * 2022-03-24 2023-09-28 Ecolab Usa Inc. Émulsifiant pour la lessive comprenant un tensioactif et un solvant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0945473A1 (fr) * 1998-03-24 1999-09-29 National Starch and Chemical Investment Holding Corporation Méthode du type "in situ" solvant-libre pour la production de copolymères greffés basés sur les anhydrides
US20040097624A1 (en) * 2000-10-20 2004-05-20 Elise Camus Amphiphilic copolymers for use in particular as emulsifying agent
WO2006016179A1 (fr) 2004-08-12 2006-02-16 The University Of Bristol Matériaux polymériques de pégosité réduite, méthodes de fabrication de ces matériaux et compositions de chewing-gum comprenant de tels matériaux
WO2008104546A1 (fr) 2007-02-26 2008-09-04 Revolymer Limited Composition de gomme à mâcher
WO2009050203A1 (fr) * 2007-10-15 2009-04-23 Revolymer Limited Synthèse sans solvant de matériau polymère amphiphile

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0945473A1 (fr) * 1998-03-24 1999-09-29 National Starch and Chemical Investment Holding Corporation Méthode du type "in situ" solvant-libre pour la production de copolymères greffés basés sur les anhydrides
US20040097624A1 (en) * 2000-10-20 2004-05-20 Elise Camus Amphiphilic copolymers for use in particular as emulsifying agent
WO2006016179A1 (fr) 2004-08-12 2006-02-16 The University Of Bristol Matériaux polymériques de pégosité réduite, méthodes de fabrication de ces matériaux et compositions de chewing-gum comprenant de tels matériaux
WO2008104546A1 (fr) 2007-02-26 2008-09-04 Revolymer Limited Composition de gomme à mâcher
WO2008104547A1 (fr) 2007-02-26 2008-09-04 Revolymer Limited Gomme à mâcher médicamentée
WO2009050203A1 (fr) * 2007-10-15 2009-04-23 Revolymer Limited Synthèse sans solvant de matériau polymère amphiphile
WO2009068570A1 (fr) 2007-11-26 2009-06-04 Revolymer Limited Materiau copolymere amphiphile
WO2009068569A1 (fr) 2007-11-26 2009-06-04 Revolymer Limited Matériau polymère amphiphile

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110337457A (zh) * 2017-02-24 2019-10-15 日本瑞翁株式会社 改性聚合物胶乳的制造方法
CN110337457B (zh) * 2017-02-24 2021-10-19 日本瑞翁株式会社 改性聚合物胶乳的制造方法
US20220268538A1 (en) * 2021-02-24 2022-08-25 Valvoline Licensing And Intellectual Property Llc Foaming evaporator coil cleaner
WO2023178580A1 (fr) * 2022-03-24 2023-09-28 Ecolab Usa Inc. Émulsifiant pour la lessive comprenant un tensioactif et un solvant

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