WO2005049783A1 - Cleaning compositions - Google Patents

Cleaning compositions Download PDF

Info

Publication number
WO2005049783A1
WO2005049783A1 PCT/GB2004/004798 GB2004004798W WO2005049783A1 WO 2005049783 A1 WO2005049783 A1 WO 2005049783A1 GB 2004004798 W GB2004004798 W GB 2004004798W WO 2005049783 A1 WO2005049783 A1 WO 2005049783A1
Authority
WO
WIPO (PCT)
Prior art keywords
compositions
oil
composition according
alkyl
composition
Prior art date
Application number
PCT/GB2004/004798
Other languages
French (fr)
Inventor
Irena Hladun
Ramakrishnan Hariharan
Andrew Arno Kloeppel
Fabio Malatesta
Original Assignee
Reckitt Benckiser Inc
Reckitt Benckiser (Uk) 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 Reckitt Benckiser Inc, Reckitt Benckiser (Uk) Limited filed Critical Reckitt Benckiser Inc
Priority to BRPI0415057-0A priority Critical patent/BRPI0415057A/en
Publication of WO2005049783A1 publication Critical patent/WO2005049783A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0089Pearlescent compositions; Opacifying agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00Compositions of detergents, not provided for by one single preceding group
    • C11D10/04Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • Cleaning compositions are commercially important products and enjoy a wide field of utility in assisting in the removal of dirt and grime from surfaces, especially those characterized as useful with "hard surfaces".
  • Hard surfaces are those which are frequently encountered in lavatories such as lavatory fixtures such as toilets, shower stalls, bathtubs, bidets, sinks, etc., as well as countertops, walls, floors, etc.
  • Such cleaning compositions are typically provided for use “as-is” wherein they are intended to be used as supplied from a manufacturer, or in "concentrate” form wherein they are intended to be diluted in a larger volume of water prior to use in the cleaning treatment of hard surfaces.
  • aqueous, dilutable hard surface cleaning compositions which comprise (preferably consists of, more preferably consisting essentially of): one or more detersive surfactants, preferably containing one or more anionic surfactants including anionic soaps optionally but preferably in conjunction with one or more nonionic surfactants; one or more thickener constituents; one or more opacifying constituents; optionally but desirably one or more organic solvents; optionally one or more constituents for improving the aesthetic or functional features of the inventive compositions; and, water.
  • the hard surface cleaning compositions of the present invention provide slightly viscous compositions which feature a desirable opacified appearance which is highly sought by consumers. Further aspects of the invention are directed to processes for the manufacture of aqueous, dilutable hard surface cleaning compositions as well as processes for the treatment of hard surfaces utilizing the aforesaid aqueous, dilutable hard surface cleaning compositions.
  • the inventive compositions necessarily comprise one or more detersive surfactants, preferably containing one or more anionic surfactants including anionic soaps optionally but preferably in conjunction with one or more nonionic surfactants
  • the detersive surfactant constituent necessarily includes at least one anionic surfactant.
  • Exemplary useful anionic surfactants such as alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of one or more of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoefher sulfates, alkylaryl polyefher sulfates, alkylaryl sulfates, alkylaryl sulfonates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alky
  • the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.
  • the alkylaryl sulfonates are preferred, of which sodium dodecylbenzene sulfonate is particularly preferred.
  • Such preferred alkylaryl sulfonates may be supplied as a constituent, or may be formed in situ by the reaction of appropriate molar amounts of sulfonic acid with a sodium comprising base material such as NaOH.
  • Anionic soap surfactants may also be present in the detersive surfactant constituent either in place of the anionic surfactant or in conjunction with the anionic surfactant described above.
  • Exemplary useful anionic soap surfactants include includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkanol- ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms.
  • Suitable fatty acids can be obtained from natural sources such as, for instance, plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof).
  • the fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by the Fischer-Tropsch process).
  • Resin acids are suitable such as rosin and those resin acids in tall oil.
  • Naphthenic acids are also suitable.
  • Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process.
  • Particularly useful is the sodium or potassium salt of the mixtures of fatty acids derived from castor oil, i.e., sodium or potassium castor oil soap.
  • the anionic soap surfactants contemplated herein the alkyl metal soaps, such as sodium soaps of naturally derived fatty acids, are preferred.
  • the detersive surfactant constituent includes one or more nonionic surfactants.
  • any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with an alkylene oxide, especially ethylene oxide or with the polyhydration product thereof, a polyalkylene glycol, especially polyethylene glycol, to form a water soluble or water dispersible nonionic surfactant compound.
  • suitable nonionic surfactants which may be used in the present invention include the following:
  • One class of useful nonionic surfactants include polyalkylene oxide condensates of alkyl phenols.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with an alkylene oxide, especially an ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • the alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene and the like.
  • Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.
  • a further class of useful nonionic surfactants include the condensation products of aliphatic alcohols with from about 1 to about 60 moles of an alkylene oxide, especially an ethylene oxide.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from about 10 to 14 carbon atoms).
  • Other examples are those C 6 -C ⁇ straight-chain alcohols which are ethoxylated with from about 3 to about 6 moles of ethylene oxide. Their derivation is well known in the art.
  • Examples include Alf nic® 810-4.5, which is described in product literature from Sasol as a C S -C ⁇ O straight-chain alcohol having an average molecular weight of 356, an ethylene oxide content of about 4.85 moles (about 60 wt.%), and an HLB of about 12; Alfbnic® 810-2, which is described in product literature as a Cs- o straight-chain alcohols having an average molecular weight of 242, an ethylene oxide content of about 2.1 moles (about 40 wt.%), and an HLB of about 12; and Alfonic® 610-3.5, which is described in product literature as having an average molecular weight of 276, an ethylene oxide content of about 3.1 moles (about 50 wt.%), and an HLB of 10.
  • alcohol ethoxylates are C 10 oxo-alcohol ethoxylates available from BASF under the Lutensol® ON tradename. They are available in grades containing from about 3 to about 11 moles of ethylene oxide (available under the names Lutensol® ON 30; Lutensol® ON 50; Lutensol® ON 60; Lutensol® ON 65; Lutensol® ON 66; Lutensol® ON 70; Lutensol® ON 80; and Lutensol®ON 110).
  • ethoxylated alcohols include the Neodol® 91 series non-ionic surfactants available from Shell Chemical Company which are described as C -C ⁇ ethoxylated alcohols.
  • Neodol® 91 series non-ionic surfactants of interest include Neodol® 91-2.5, Neodol® 91-6, and Neodol® 91-8.
  • Neodol® 91-2.5 has been described as having about 2.5 ethoxy groups per molecule;
  • Neodol 91-6 has been described as having about 6 ethoxy groups per molecule;
  • Neodol 91-8 has been described as having about 8 ethoxy groups per molecule.
  • Further examples of ethoxylated alcohols include the Rhodasurf® DA series non-ionic surfactants available from Rhodia which are described to be branched isodecyl alcohol ethoxylates.
  • Rhodasurf® DA-530 has been described as having 4 moles of ethoxylation and an HLB of 10.5; Rhodasurf® DA-630 has been described as having 6 moles of ethoxylation with an HLB of 12.5; and Rhodasurf® DA-639 is a 90% solution of DA- 630.
  • ethoxylated alcohols include those from Tomah Products (Milton, WI) under the Tomadol® tradename with the formula RO(CH 2 CH 2 O) n H where R is the primary linear alcohol and n is the total number of moles of ethylene oxide.
  • the ethoxylated alcohol series from Tomah include 91-2.5; 91-6; 91-8 - where R is linear CyCio/Cn and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; where R is linear C n and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5 - where R is linear C 12 /C 13 and n is 1, 3, 5, or 6.5; 25-3; 25-7; 25-9; 25-12 - where R is linear C 12 /C 13 /C 1 / C 15 and n is 3, 7, 9, or 12; and 45-7; 45- 13 - where R is linear C 1 / C 15 and n is 7 or 13.
  • a further class of useful nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C 6 -C 18 alcohols which further include an average of from 2 to 80 moles of ethoxylation per mol of alcohol. These examples include the Genapol® UD (ex.
  • Genapol® UD 030 C ⁇ -oxo-alcohol polyglycol ether with 3 EO
  • Genapol® UD 050 C ⁇ -oxo-alcohol polyglycol ether with 5 EO
  • Genapol® UD 070 C ⁇ - oxo-alcohol polyglycol ether with 7 EO
  • Genapol® UD 080 C ⁇ -oxo-alcohol polyglycol ether with 8 EO
  • Genapol® UD 110 C ⁇ -oxo-alcohol polyglycol ether with 11 EO.
  • Exemplary useful nonionic surfactants include the condensation products of a secondary aliphatic alcohols containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • Examples of commercially available nonionic detergents of the foregoing type are those presently commercially available under the trade name of Tergitol® such as Tergitol 15-S-12 which is described as being C ⁇ - C 15 secondary alkanol condensed with 9 ethylene oxide units, or Tergitol 15-S-9 which is described as being C ⁇ -C 15 secondary alkanol condensed with 12 ethylene oxide units per molecule.
  • a further class of useful nonionic surfactants include those surfactants having a formula: RO(CH 2 CH 2 0)nH wherein; R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C 12 H 25 to C 16 H 33 and n represents the number of ethoxy repeating units and is a number of from about 1 to about 12.
  • Surfactants of this formula are presently marketed under the Genapol® tradename (ex.
  • surfactants include the "26-L” series of the general formula RO(CH 2 CH 2 0) n H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C 12 H 25 to C 16 H 33 and n represents the number of repeating units and is a number of from 1 to about 12, such as 26-L-l, 26-L-1.6, 26-L-2, 26-L-3, 26-L-5, 26- L-45, 26-L-50, 26-L-60, 26-L-60N, 26-L-75, 26-L-80, 26-L-98N, and the 24-L .series, derived from synthetic sources and typically contain about 55% C 12 and 45% C 14 alcohols, such as 24-L-3, 24-L-45, 24-L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N, all sold under the Genapol® tradename.
  • a further class of useful nonionic surfactants include alkoxy block copolymers, and in particular, compounds based on ethoxy/propoxy block copolymers.
  • Polymeric alkylene oxide block copolymers include nonionic surfactants in which the major portion of the molecule is made up of block polymeric C 2 -C 4 alkylene oxides.
  • Such nonionic surfactants while preferably built up from an alkylene oxide chain starting group, and can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, thiols and secondary alcohols.
  • One group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A):
  • EO ethylene oxide
  • PO propylene oxide
  • y equals at least 15
  • (EO) x +y 20 to 50% of the total weight of said compounds, and, the total molecular weight is preferably in the range of about 2000 to 15,000.
  • PLURONIC ex. BASF
  • Emulgen ex. Kao.
  • a further group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those can be represented by the formula (B):
  • R is an alkyl, aryl or aralkyl group, where the R group contains 1 to 20 carbon atoms, the weight percent of EO is within the range of 0 to 45% in one of the blocks a, b, and within the range of 60 to 100% in the other of the blocks a, b, and the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and 5 to 100 moles in the EO rich block.
  • Specific nonionic surfactants which in general are encompassed by Formula B include butoxy derivatives of propylene oxide/ethylene oxide block polymers having molecular weights within the range of about 2000-5000. Still further examples of useful nonionic surfactants include those which can be represented by formula (C) as follows: RO-(BO)n(EO) x -H (C)
  • EO represents ethylene oxide
  • BO represents butylene oxide
  • R is an alkyl group containing I to 20 carbon atoms
  • n is about 5-15
  • x is about 5-15.
  • nonionic surfactants include those which may be represented by the following formula (D): HO-(EO) ⁇ (BO) n (EO) y -H (D)
  • EO represents ethylene oxide
  • BO represents butylene oxide
  • n is about 5-15, preferably about 15
  • x is about 5-15, preferably about 15, and y is about 5-15, preferably about 15.
  • Still further exemplary useful nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which maybe represented by the following formula:
  • (EO) represents ethoxy
  • (PO) represents propoxy
  • the amount of (PO) x is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500
  • the amount of (EO) y is such as to provide about 20% to 90% of the total weight of said compound.
  • Further useful non-ionic surfactants which may be used in the inventive compositions include those presently marketed under the trade name Pluronics® (ex. BASF).
  • the compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
  • the molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4,000 and preferably 200 to 2,500.
  • polyoxyethylene radicals of the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble.
  • the molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight.
  • these surfactants are in liquid form and particularly satisfactory surfactants are available as those marketed as Pluronics® L62 and Pluronics® L64.
  • Alkylmonoglycosides and alkylpolyglycosides which find use in the present inventive compositions include known nonionic surfactants which are alkaline and electrolyte stable.
  • Alkylmonoglycosides and alkylpolyglycosides are prepared generally by reacting a monosaccharide, or a compound hydrolyzable to a monosaccharide with an alcohol such as a fatty alcohol in an acid medium.
  • a monosaccharide or a compound hydrolyzable to a monosaccharide with an alcohol such as a fatty alcohol in an acid medium.
  • alcohol such as a fatty alcohol in an acid medium.
  • Various glycoside and polyglycoside compounds including alkoxylated glycosides and processes for making them are disclosed in U.S. Pat. Nos. 2,974,134; 3,219,656; 3,598,865; 3,640,998; 3,707,535, 3,772,269; 3,839,318; 3,974,138; 4,223,129 and 4,528,106 the contents of which are incorporated by reference.
  • R 2 is a hydrophobic group selected from alkyl groups, alkylphenyl groups, hydroxyalkylphenyl groups as well as mixtures thereof, wherein the alkyl groups may be straight chained or branched, and which contain from about 8 to about 18 carbon atoms, n has a value of 2 - 8, especially a value of 2 or 3; r is an integer from 0 to 10, but is preferably 0, Z is derived from glucose; and, x is a value from about 1 to 8, preferably from about 1.5 to 5.
  • the alkylpolyglycosides are nonionic fatty alkylpolyglucosides which contain a straight chain or branched chain C 8 -C 15 alkyl group, and have an average of from about 1 to 5 glucose units per fatty alkylpolyglucoside molecule. More preferably, the nonionic fatty alkylpolyglucosides which contain straight chain or branched C 8 -C 15 alkyl group, and have an average of from about 1 to about 2 glucose units per fatty alkylpolyglucoside molecule.
  • a further exemplary group of alkyl glycoside surfactants suitable for use in the practice of this invention may be presented by the following formula (A): RO-(R 1 O) y -(G) x Zb (A) wherein: R is a monovalent organic radical containing from about 6 to about 30, preferably from about 8 to 18 carbon atoms,
  • Ri is a divalent hydrocarbon radical containing from about 2 to about 4 carbon atoms
  • y is a number which has an average value from about 0 to about 1 and is preferably 0,
  • G is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; and, x is a number having an average value from about 1 to 5 (preferably from 1.1 to 2); O II
  • Z is O 2 M 1 , ° ⁇ C-R2 5 0 (CH 2 ), CO 2 M 1 , OSO 3 M 1 , or ; R 2 is (CH 2 )CO 2 M 1 or ; (with the proviso that Z can be OzM 1 only if Z is in place of a primary hydroxyl group in which the primary hydroxyl-bearing carbon atom, O
  • R is generally the residue of a fatty alcohol having from about 8 to 30 and preferably 8 to 18 carbon atoms.
  • alkylglycosides examples include, for example APG 325 CS Glycoside® which is described as being a 50% C 9 -C ⁇ alkyl polyglycoside, also commonly referred to as D- glucopyranoside, (commercially available from Henkel KGaA) and Glucopon® 625 CS which is described as being a 50% o -C 16 alkyl polyglycoside, also commonly referred to as a D-glucopyranoside, (ex. Henkel), well as Glucopon® 225DK, a further alkylpolyglycoside which is more specifically described as being 68 - 72%wt.
  • APG 325 CS Glycoside® which is described as being a 50% C 9 -C ⁇ alkyl polyglycoside, also commonly referred to as D- glucopyranoside, (commercially available from Henkel KGaA)
  • Glucopon® 625 CS which is described as being a 50%
  • alkyl ⁇ (+b) mono- and oligo- C 8 -C 10 glucopyranosides (ex. Henkel) which is derived from glucose derivatives of maize, and fatty alcohols derived from coconut and palm kern oils.
  • alkyl polyglycosides having differing carbon chain lengths include those currently marketed under the tradename Glucopon 220, Glucopon 225, Glucopon 425, Glucopon 600, and Glucopon 625, all available from Henkel Corporation
  • Glucopon 220, Glucopon 225, Glucopon 425, Glucopon 600, and Glucopon 625 all available from Henkel Corporation
  • Further nonionic surfactants which may be included in the inventive compositions include alkoxylated alkanolamides, preferably C 8 -C 24 alkyl di(C -C 3 alkanol amides), as represented by the following formula: R 5 -CO-NH-R 6 -OH wherein R 5 is a branched or straight chain Cs-C 24 alkyl radical, preferably a Cio-Ci ⁇ alkyl radical and more preferably a C 12 -C 1 alkyl radical, and Re is a C 1 -C 4 alky
  • the detersive surfactant constituent necessarily comprises a nonionic surfactant based on a linear primary alcohol ethoxylate particularly wherein the alkyl portion is a C 8 to C 16 , but particularly a C 9 to C ⁇ alkyl group, and having an average of between about 6 to about 8 moles of ethoxylation.
  • the detersive surfactant constituent according to the invention desirably includes at least one anionic surfactant and/or anionic soap surfactant in conjunction with at least one nonionic surfactant, particularly a nonionic surfactant derived from alcohol alkoxylates.
  • the detersive surfactant constituent of the present invention comprises from about 0.1 to about 30 wt%, preferably from about 1 to about 20 wt%, and more preferably from about 2 to about 10 wt% of the dilutable hard surface cleaning composition of which they form a part.
  • the dilutable hard surface cleaning compositions of the invention necessarily include at least one thickener constituent.
  • Thickeners useful in the present invention to achieve this viscosity are selected from the group consisting of polysaccharide polymers selected from cellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses, carboxy alkyl hydroxy alkyl celluloses, naturally occurring polysaccharide polymers such as xanthan gum, guar gum, locust bean gum, tragacanth gum, or derivatives thereof, polycarboxylate polymers, polyacrylamides, clays, and mixtures thereof.
  • polysaccharide polymers selected from cellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses, carboxy alkyl hydroxy alkyl celluloses, naturally occurring polysaccharide polymers such as xanthan gum, guar gum, locust bean gum,
  • cellulose derivatives examples include methyl cellulose ethyl cellulose, hydroxymethyl cellulose hydroxy ethyl cellulose, hydroxy propyl cellulose, carboxy methyl cellulose, carboxy methyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy propyl methyl cellulose, ethylhydroxymethyl cellulose and ethyl hydroxy ethyl cellulose.
  • Exemplary polycarboxylate polymers thickeners have a molecular weight from about 500,000 to about 4,000,000, preferably from about 1,000,000 to about 4,000,000, with, preferably, from about 0.5% to about 4% crosslinking.
  • Preferred polycarboxylate polymers include polyacrylate polymers including those sold under trade names Carbopol®, Acrysol® ICS-1 and Sokalan®.
  • the preferred polymers are polyacrylates.
  • Other monomers besides acrylic acid can be used to form these polymers including such monomers as ethylene and propylene which act as diluents, and maleic anhydride which acts as a source of additional carboxylic groups.
  • the polycarboxylate polymer can be a non-associative thickener or stabilizer, such as a homopolymer or a copolymer of an olefinically unsaturated carboxylic acid or anhydride monomers containing at least one activated carbon to carbon olefinic double bond and at least one carboxyl group or an alkali soluble acrylic emulsion, or an associative thickener or stabilizer, such as a hydrophobically modified alkali soluble acrylic emulsion or a hydrophobically modified nonionic polyol polymer, i.e., a hydrophobically modified urethane polymer, or combinations thereof.
  • a non-associative thickener or stabilizer such as a homopolymer or a copolymer of an olefinically unsaturated carboxylic acid or anhydride monomers containing at least one activated carbon to carbon olefinic double bond and at least one carboxyl group or an alkali
  • the copolymers are preferably of a polycarboxylic acid monomer and a hydrophobic monomer.
  • the preferred carboxylic acid is acrylic acid.
  • the homopolymers and copolymers preferably are crosslinked. Homopolymers of polyacrylic acid are described, for example, in U.S. Pat. No. 2,798,053. Examples of homopolymers which are useful include Carbopol® 934, 940, 941, Ultrez 10, ETD 2050, and 974P polymers, which are available from Noveon.
  • Such polymers are homopolymers of unsaturated, polymerizable carboxylic monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and the like.
  • Hydrophobically modified polyacrylic acid polymers are described, for example, in U.S. Pat. Nos. 3,915,921, 4,421,902, 4,509,949, 4,923,940, 4,996,274, 5,004,598, and 5,349,030. These polymers have a large water-loving hydrophilic portion (the polyacrylic acid portion) and a smaller oil-loving hydrophobic portion (which can be derived from a long carbon chain acrylate ester).
  • Representative higher alkyl acrylic esters are decycl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate and melissyl acrylate, and the corresponding methacrylates.
  • carboxylic monomer and more than one acrylate ester or vinyl ester or ether or styrenic can be used in the monomer charge.
  • the polymers can be dispersed in water and neutralized with base to thicken the aqueous composition, form a gel, or emulsify or suspend a deliverable.
  • Useful polymers are sold as Carbopol® 1342 and 1382 and Pemulen® TR-1, TR-2, 1621, and 1622, all available from Noveon.
  • the carboxyl containing polymers are prepared from monomers containing at least one activated vinyl group and a carboxyl group, and would include copolymers of polymerizable carboxylic monomers with acrylate esters, acrylamides, alkylated acrylamides, olefins, vinyl esters, vinyl ethers, or styrenics.
  • the carboxyl containing polymers have molecular weights greater than about 500 to as high as several billion, or more, usually greater than about 10,000 to 900,000 or more.
  • inte olymers of hydrophobically modified monomers and steric stabilizing polymeric surface active agents having at least one hydrophilic moiety and at least one hydrophobic moiety or a linear block or random comb configuration or mixtures thereof are also useful.
  • steric stabilizers which can be used are Hypermer®, which is a poly(12-hydroxystearic acid) polymer, available from Imperial Chemical Industries Inc. and Pecosil®, which is a mefhyl-3-polyethoxypropyl siloxane- ⁇ -phosphate polymer, available from Phoenix Chemical, Somerville, N.J.
  • the polymers can be crosslinked in a manner known in the art by including, in the monomer charge, a suitable crosslinker in amount of about 0.1 to 4%, preferably 0.2 to 1% by weight based on the combined weight of the carboxylic monomer and the comonomer(s).
  • the crosslinker is selected from polymerizable monomers which contain a polymerizable vinyl group and at least one other polymerizable group.
  • Polymerization of the carboxyl-containing monomers is usually carried out in a catalyzed, free radical polymerization process, usually in inert diluents, as is known in the art.
  • polycarboxylic acid polymer compositions which can be employed include, for example, crosslinked copolymers of acrylates, (meth)acrylic acid, maleic anhydride, and various combinations thereof.
  • Commercial polymers are available from Rheox Inc., Highstown, N.J.
  • Clay thickeners comprise, for example, colloid-forming clays, for example, such as smectite and/or attapulgite types.
  • the clay materials can be described as expandable layered clays, i.e., aluminosilicates and magnesium silicates.
  • expandable as used to describe the instant clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water.
  • the expandable clays used herein are those materials classified geologically as smectites (or montmorillonite) and attapulgites (or polygorskites).
  • Smectites are three-layered clays. There are two distinct classes of smectite-type clays. In the first, aluminum oxide is present in the silicate crystal lattice; in the second class of smectites, magnesium oxide is present in the silicate crystal lattice.
  • the general formulas of these smectites are Al (Si 2 O 5 ) 2 (OH) 2 and Mg 3 (Si 2 O 5 )(OH) 2 , for the aluminum and magnesium oxide type clays, respectively.
  • the range of the water of hydration in the above formulas may vary with the processing to which the clay has been subjected.
  • Commercially available clays include, for example, montmorillonite, bentonite, volchonskoite, nontronite, beidellite, hectorite, saponite, sauconite and vermiculite.
  • the clays herein are available under various trade names such as Gelwhite GP, Gelwhite H, Mineral Colloid BP, and Laponite from Southern Clay Products, Inc., Texas; and Van Gel O from R. T. Vanderbilt.
  • Gelwhite H-NF has a typical chemical analysis of SiO 2 66.5%; Al 2 O 3 14.7%; MgO 3.2%; Fe 2 O 3 0.8%; CaO 2.2%; Na 2 O 3.3%; K 2 O 0.1%; TiO 2 0.2%.
  • Gelwhite L-NF has a typical chemical analysis of SiO 2 66.5%; Al 2 O 3 14.7%; MgO .3.2%; Fe 2 O 3 0.8%; CaO 2.2%; Na 2 O 3.3%; K 2 O 0.1%; TiO 2 0.2%.
  • Gelwhite GP has a typical chemical analysis of SiO 2 66.5%; Al 2 O 3 14.7%; MgO 3.2%; Fe 2 O 3 0.8%; CaO 2.2%; Na 2 O 3.3%; K 2 O 0.1%; TiO 2 0.2%.
  • Mineral Colloid BP has a typical chemical analysis of Si0 2 62.9%; Al 2 O3 17.1%; MgO 2.4%; Fe 2 O 3 4.8%; CaO 0.7%; Na 2 O 2.1%; K 2 O 0.2%; TiO 2 0.1%.
  • a second type of expandable clay material useful in the instant invention is classified geologically as attapulgite (polygorskite). Attapulgites are magnesium-rich clays having principles of superposition of tetrahedral and octahedral unit cell elements different from the smectites.
  • Attapulgite clays are commercially available. For example, such clays are marketed under the tradename Attagel, i.e. Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals & Chemicals Corporation.
  • the preferred clay thickeners comprise the inorganic, colloid forming clays of smectite and/or attapulgite types. Preferred clays include products from Vanderbilt Chemical Company such as VanGel O.
  • the amount of thickener used in the present invention can range from about 0.1 to
  • inventive compositions exhibit a viscosity greater than that of water, and desirably exhibit a viscosity of at least about 50 cps. More preferably the inventive compositions exhibit a viscosity of from about 50 cps to about 2000 cps, but most preferably exhibit a viscosity of between about 300 cps and 700 cps, and most particularly of about 500 cps.
  • inventive compositions need be maintained in a thickened state in order to provide sufficient suspension of the at least one opacifying agent present.
  • the dilutable hard surface cleaning compositions of the invention necessarily include at least one opacifying constituent.
  • Such materials are typically either polymers, oleochemical fatty dispersions or minerals such as mica.
  • Exemplary useful and preferred materials include alkylene glycol mono- and di-stearates particularly Ci-C ⁇ glycol mono- and di-stearates, especially ethylene glycol monostearate, ethylene glycol distearate and propylene glycol monostearate, presently commercially available as Sipoest® materials, glycerol mono- and di-stearate.
  • Further useful materials which may be used to impart an opacifying and pearlescent appearance to the inventive compositions are those presently commercially available as Euperlan® materials.
  • Euperlan® PK 771 and Euperlan® PK 810 both described to be a mixture of sodium laureth sulfate, glycol distearate, cocoamine monoethanolamine and laureth-10
  • Euperlan® PK 900 described to be a mixture of PEG-3 distearate and sodium laureth sulfate
  • Euperlan® PK 1200 described to be a mixture of coco-glucoside, glycol distearate and glycerin
  • Euperlan® PK 3000 and Euperlan® PK 4000 both described to be a mixture of glycol distearate, laureth-4 and cocoamidopropyl betaine.
  • the specific opacifying constituent should be selected to be compatible with the detersive surfactant constituent. Typically the amount of the opacifying constituent used in the present invention can range from about 0.1 to 10 wt%. While optional, in preferred embodiments the present inventive compositions comprise one or more water soluble or water dispersible organic solvents. Exemplarly useful water soluble organic solvents include short chain -Ce alcohols, glycol ethers, and mixtures thereof. Such water soluble organic solvents provide effective solubilization of many types of greases and fats which may be encountered in soils on hard surfaces.
  • organic solvents may be used as the organic solvent constituent according to the invention.
  • short chain alcohols include ethanol, propanol, and isopropanol.
  • useful glycol ethers include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, diethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, and mixtures thereof.
  • the glycol ethers are preferred, and particularly preferred are compositions wherein the organic solvent constituent is solely one or more glycol ethers.
  • the water soluble organic solvent constituent may be present in the inventive compositions in amounts of from about 0.1 to about 20 wt%, preferably in amounts of from about 0.5 to about 10 wt%.
  • the compositions of the present invention can also optionally comprise one or more further constituents which are directed to improving the aesthetic or functional features of the inventive compositions.
  • further constituents include one or more coloring agents, fragrances and fragrance solubilizers, other surfactants, pH adjusting agents and pH buffers including organic and inorganic salts, optical brighteners, hydrotropes, antifoaming agents, anti-oxidants, AND preservatives.
  • the esthetic and consumer appeal of the product is often favorably improved.
  • the use and selection of these optional constituents is well known to those of ordinary skill in the art.
  • the one or more optional constituents present in the inventive compositions do not exceed about 10%wt, preferably do not exceed 5%wt.
  • the compositions according to the invention optionally but desirably include an amount of a pH adjusting agent or pH buffer composition. Such compositions include many which are known to the art and which are conventionally used.
  • pH adjusting agents include phosphorus containing compounds, monovalent and polyvalent salts such as of silicates, carbonates, and borates, certain acids and bases, tartrates and certain acetates.
  • Further exemplary pH adjusting agents include mineral acids, basic compositions, and organic acids, which are typically required in only minor amounts.
  • pH buffering compositions include the alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates, bicarbonates, polycarbonateshydroxides, and mixtures of the same.
  • compositions according to the invention include an effective amount of an organic acid and/or an inorganic salt form thereof which may be used to adjust and maintain the pH of the compositions of the invention to the desired pH range.
  • Particularly useful is are carbonates and bicarbonates and particularly and metal salts thereof such as sodium carbonate, sodium bicarbonate which are widely available and which are effective in providing pH adjustment and buffering effects.
  • the pH of the inventive compositions are alkaline, desirably in excess of 7, more desirably the pH of the compositions are 8 or greater, still more preferably are about 9 or greater.
  • constituents are one or more coloring agents which find use in modifying the appearance of the compositions and enhance their appearance from the perspective of a consumer or other end user.
  • Known coloring agents may be incorporated in the compositions in any effective amount to improve or impart to compositions a desired appearance or color.
  • Such a coloring agent or coloring agents may be added in a conventional fashion, i.e., admixing to a composition or blending with other constituents used to form a composition.
  • Such coloring agent may be based on naturally occurring coloring agents, or may be based on one or more synthetically produced materials including synthetic dyes and pigments particularly those recited in the Color Index.
  • Further optional, but desirable constituent include fragrances, natural or synthetically produced.
  • fragrances may be added in any conventional manner, admixing to a composition or blending with other constituents used to form a composition, in amounts which are found to be useful to enhance or impart the desired scent characteristic to the composition, and/or to cleaning compositions formed therefrom.
  • Exemplary useful fragrances include those based on digeranyl succinate, dineryl succinate, geranyl neryl succinate, geranyl phenylacetate, neryl phenylacetate, geranyl laurate, neryl laurate, di(b-citronellyl) maleate, dinonadol maleate, diphenoxyanol maleate, di(3,7-dimethyl-l-octanyl) succinate, di(cyclohexylethyl) maleate, diflralyl succinate, di(phenylethyl) adipate, 7-acetyl-l,2,3,4,5,6,7,8-octahydro- 1,1,6,7-tetramethyl naphthalene, ionone methyl, ionone gamma methyl, methyl cedrylone, methyl dihydrojasmonate, methyl l,6,10-trimethyl-2,5,9-cyclodo
  • the fragrance constituent may also be based on one or more essential oils including one or more selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Canaga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69°C (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil,
  • fragrance compounds not particularly eludicated here but which are found useful in providing a desirable fragrancing effect may also be included in the inventive compositions.
  • the fragrance constituent maybe included in any effective amount, and of course mixtures of two or more fragrance compounds may be used to provide the fragrance constituent.
  • the fragrance constituent in present in an amount not exceeding 5%wt. of the inventive composition of which it forms a part, and more preferably is present in an amount not exceeding 1 %wt.
  • a fragrance solubilizer which assists in the dispersion, solution or mixing of the fragrance constituent in an aqueous base.
  • nonionic surfactants include water soluble nonionic surfactants of which many are commercially known and by way of non-limiting example include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates on primary alkanols, and condensates of ethylene oxide with sorbitan fatty acid esters.
  • This fragrance solubilizer component is added in minor amounts, particularly amount which are found effective in aiding in the solubilization of the fragrance component, but not in any significantly greater proportion, such that it would be considered as a surfactant constituent.
  • Such minor amounts of fragrance solubilizer recited herein is generally up to about 0.2% by weight of the fragrance constituent in the inventive compositions but is more generally an amount of about 0.1%) by weight and less, and preferably is present in amounts of about 0.05% by weight and less.
  • the inventive compositions optionally but desirably comprise a preservative constituent. Since a significant portion of the inventive compositions comprise water, it is preferably that the preservative be water soluble.
  • the selected water soluble preservatives are those which exhibit stability and efficacy in the aqueous compositions according to the invention at neutral, but preferably at alkaline pH's especially in the preferred pH ranges noted above.
  • Such water soluble preservatives include compositions which include parabens, including methyl parabens and ethyl parabens, glutaraldehyde, formaldehyde, 2-bromo-2-nitropropoane-l,3-diol, 5-chloro-2-methyl-4-isothiazolin-3- one, 2-methyl-4-isothiazoline-3-one, and mixtures thereof.
  • One exemplary composition is a combination 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3- one where the amount of either component may be present in the mixture anywhere from 0.001 to 99.99 weight percent, based on the total amount of the preservative.
  • the most preferred preservative are those commercially available preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2- methyl-4-isothiazolin-3-one marketed under the trademark KATHON® CG ICP as a preservative composition presently commercially available from Rohm and Haas (Philadelphia, PA).
  • preservative compositions include KATHON® CG/ICP II, a further preservative composition presently commercially available from Rohm and Haas (Philadelphia, PA), PROXEL® which is presently commercially available from Zeneca Biocides (Wilmington, DE), SUTTOCIDE® A which is presently commercially available from Sutton Laboratories (Chatam, NJ) as well as TEXTAMER® 38 AD which is presently commercially available from Calgon Corp. (Pittsburgh, PA).
  • the preservative constituent is present in the dilutable hard surface cleaning compositions of the present invention in any amount which is effective in retarding or eliminating the growth of undesired microorganisms in the inventive compositions particularly upon standing.
  • the preservative constituent need be present in only minor amounts, and is advantageously present in amounts for from about 0.001%wt.
  • the preservative constituent is necessarily present.
  • water forms a major constituent. Water is added in order to provide 100 wt% of the concentrate composition.
  • the water may be tap water, but is preferably distilled and/or deionized water. If the water is tap water, it is preferably appropriately filtered in order to remove any undesirable impurities such as organics or inorganics, especially mineral salts which are present in hard water which may thus interfere with the operation of the other constituents of the invention, as well as any other optional components of the liquid concentrates according to the invention.
  • compositions according to the invention are useful in the cleaning of surfaces, especially hard surfaces in need of such treatment.
  • cleaning of such surfaces comprises the step of applying a stain releasing effective amount of a composition as taught herein to such a stained surface.
  • the compositions are optionally but desirably wiped, scrubbed or otherwise physically contacted with the hard surface, and further optionally, may be subsequently rinsed from such a cleaned hard surface.
  • inventive compositions described herein may be provided as a ready to use product which may be directly applied to a hard surface, it is desirably provided in a concentrated form intended to be diluted in water to form a cleaning composition therefrom.
  • concentrate and “concentrate composition” in this specification and claims is the pre-consumer dilution and composition of the cleaning composition which is the essentially the form of the product prepared for sale to the consumer or other end user with required product shelf life. Such a consumer or other end user would then normally be expected to dilute the same with water to form a cleaning composition. It is to be understood however that nothing in this invention would bar its use as cleaning composition without any further dilution and it may be used in the concentrations in which it was prepared for sale.
  • cleaning compositions are the water diluted compositions which are expected to be prepared by the consumer or other end user by mixing a measured amount of the "concentrate” with water in order to form an appropriately diluted cleaning composition which is suitable for use in cleaning applications, especially in the cleaning of hard surfaces. It is also to be understood, that proportions of one or more constituents have been and generally are referred to as percent by weight or as parts by weight based on a measure of 100% by weight, unless otherwise indicated. As generally denoted above, the formulations according to the invention include both cleaning compositions and concentrates as outlined above which differ only in the relative proportion of water to that of the other constituents forming such formulations.
  • the concentrated form of the cleaning compositions find use in their original form, they are more frequently used in the formation of a cleaning composition therefrom. Such may be easily prepared by diluting measured amounts of the concentrate compositions in water by the consumer or other end user in certain weight ratios of concentrate:water, and optionally, agitating the same to ensure even distribution of the concentrate in the water.
  • the concentrate may be used without dilution, i.e., in concentrate:water concentrations of 1:0, to extremely dilute dilutions such as 1:200.
  • the concentrate is diluted in the range of 1:0.1-1:100, preferably in the range of 1:10-1:50.
  • the actual dilution selected is in part determinable by the degree and amount of dirt and grime to be removed from a surface(s), the amount of mechanical force imparted to remove the same, as well as the observed efficacy of a particular dilution. Generally better results and faster removal is to be expected at lower relative dilutions of the concentrate in water.
  • the following examples illustrate an exemplary formulation of the invention and particular preferred embodiments of the inventive compositions.
  • the terms "parts by weight” or “percentage weight” as well as “%wt.” are used interchangeably in the specification and in the following Examples wherein the weight percentages of each of the individual constituents are indicated in weight percent based on the total weight of the composition, unless indicated otherwise.
  • Example Preparation of Example Formulations Exemplary formulations illustrating certain preferred embodiments of the inventive compositions and described in more detail in Table 1 below were formulated generally in accordance with the following protocol. These constituents were used "as is" from their respective supplier. Into a suitably sized vessel, a measured amount of water was provided after which the constituents were added in no specific or uniform sequence, which indicated that the order of addition of the constituents was not critical. All of the constituents were supplied at room temperature, and any remaining amount of water was added thereafter. Mixing of the constituents was achieved by the use of a mechanical stirrer with a small diameter propeller at the end of its rotating shaft. Mixing, which generally lasted from 5 minutes to 120 minutes was maintained until the particular exemplary formulation appeared to be homogeneous. The exemplary compositions were readily pourable, and retained well mixed characteristics (i.e., stable mixtures) upon standing for extend periods. The compositions of the example formulations are listed on Table 1.
  • composition according to Example 1 provided good cleaning of hard surfaces when used without further dilution, as well as when diluted in further ratios of composition:water of 1:20 and 1:50 . While the invention is susceptible of various modifications and alternative forms, it is to be understood that specific embodiments thereof have been shown by way of example in the drawings which are not intended to limit the invention to the particular forms disclosed; on the contrary the intention is to cover all modifications, equivalents and alternatives falling within the scope and spirit of the invention as expressed in the appended claims.

Abstract

Aqueous, dilutable hard surface cleaning compositions which comprise one or more anionic and/or nonionic surfactants, a thickener and an opacifying constituent particularly wherein the opacifying constituent also provides a pearlescent effect to the compositions are disclosed.

Description

CLEANING COMPOSITIONS Cleaning compositions are commercially important products and enjoy a wide field of utility in assisting in the removal of dirt and grime from surfaces, especially those characterized as useful with "hard surfaces". Hard surfaces are those which are frequently encountered in lavatories such as lavatory fixtures such as toilets, shower stalls, bathtubs, bidets, sinks, etc., as well as countertops, walls, floors, etc. Such cleaning compositions are typically provided for use "as-is" wherein they are intended to be used as supplied from a manufacturer, or in "concentrate" form wherein they are intended to be diluted in a larger volume of water prior to use in the cleaning treatment of hard surfaces. While the art is replete with various hard surface cleaning formulations which provide some cleaning benefit there is nonetheless a real and continuing need in the art for further improved hard surface cleaning compositions. In one aspect the present invention relates to aqueous, dilutable hard surface cleaning compositions which comprise (preferably consists of, more preferably consisting essentially of): one or more detersive surfactants, preferably containing one or more anionic surfactants including anionic soaps optionally but preferably in conjunction with one or more nonionic surfactants; one or more thickener constituents; one or more opacifying constituents; optionally but desirably one or more organic solvents; optionally one or more constituents for improving the aesthetic or functional features of the inventive compositions; and, water. The hard surface cleaning compositions of the present invention provide slightly viscous compositions which feature a desirable opacified appearance which is highly sought by consumers. Further aspects of the invention are directed to processes for the manufacture of aqueous, dilutable hard surface cleaning compositions as well as processes for the treatment of hard surfaces utilizing the aforesaid aqueous, dilutable hard surface cleaning compositions. The inventive compositions necessarily comprise one or more detersive surfactants, preferably containing one or more anionic surfactants including anionic soaps optionally but preferably in conjunction with one or more nonionic surfactants The detersive surfactant constituent necessarily includes at least one anionic surfactant. Exemplary useful anionic surfactants such as alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of one or more of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoefher sulfates, alkylaryl polyefher sulfates, alkylaryl sulfates, alkylaryl sulfonates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl isethionates, and N-acyl taurates. Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms. Of these anionic surfactants, the alkylaryl sulfonates are preferred, of which sodium dodecylbenzene sulfonate is particularly preferred. Such preferred alkylaryl sulfonates may be supplied as a constituent, or may be formed in situ by the reaction of appropriate molar amounts of sulfonic acid with a sodium comprising base material such as NaOH. Anionic soap surfactants may also be present in the detersive surfactant constituent either in place of the anionic surfactant or in conjunction with the anionic surfactant described above. Exemplary useful anionic soap surfactants include includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkanol- ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Suitable fatty acids can be obtained from natural sources such as, for instance, plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof). The fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by the Fischer-Tropsch process). Resin acids are suitable such as rosin and those resin acids in tall oil. Naphthenic acids are also suitable. Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful is the sodium or potassium salt of the mixtures of fatty acids derived from castor oil, i.e., sodium or potassium castor oil soap. Of the anionic soap surfactants contemplated herein, the alkyl metal soaps, such as sodium soaps of naturally derived fatty acids, are preferred. Optionally but in many instances desirably, the detersive surfactant constituent includes one or more nonionic surfactants. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with an alkylene oxide, especially ethylene oxide or with the polyhydration product thereof, a polyalkylene glycol, especially polyethylene glycol, to form a water soluble or water dispersible nonionic surfactant compound. By way of non- limiting example, particularly examples of suitable nonionic surfactants which may be used in the present invention include the following: One class of useful nonionic surfactants include polyalkylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with an alkylene oxide, especially an ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene and the like. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol. A further class of useful nonionic surfactants include the condensation products of aliphatic alcohols with from about 1 to about 60 moles of an alkylene oxide, especially an ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from about 10 to 14 carbon atoms). Other examples are those C6 -Cπ straight-chain alcohols which are ethoxylated with from about 3 to about 6 moles of ethylene oxide. Their derivation is well known in the art. Examples include Alf nic® 810-4.5, which is described in product literature from Sasol as a CS-CΪO straight-chain alcohol having an average molecular weight of 356, an ethylene oxide content of about 4.85 moles (about 60 wt.%), and an HLB of about 12; Alfbnic® 810-2, which is described in product literature as a Cs- o straight-chain alcohols having an average molecular weight of 242, an ethylene oxide content of about 2.1 moles (about 40 wt.%), and an HLB of about 12; and Alfonic® 610-3.5, which is described in product literature as having an average molecular weight of 276, an ethylene oxide content of about 3.1 moles (about 50 wt.%), and an HLB of 10. Other examples of alcohol ethoxylates are C10 oxo-alcohol ethoxylates available from BASF under the Lutensol® ON tradename. They are available in grades containing from about 3 to about 11 moles of ethylene oxide (available under the names Lutensol® ON 30; Lutensol® ON 50; Lutensol® ON 60; Lutensol® ON 65; Lutensol® ON 66; Lutensol® ON 70; Lutensol® ON 80; and Lutensol®ON 110). Other examples of ethoxylated alcohols include the Neodol® 91 series non-ionic surfactants available from Shell Chemical Company which are described as C -Cπ ethoxylated alcohols. The Neodol® 91 series non-ionic surfactants of interest include Neodol® 91-2.5, Neodol® 91-6, and Neodol® 91-8. Neodol® 91-2.5 has been described as having about 2.5 ethoxy groups per molecule; Neodol 91-6 has been described as having about 6 ethoxy groups per molecule; and Neodol 91-8 has been described as having about 8 ethoxy groups per molecule. Further examples of ethoxylated alcohols include the Rhodasurf® DA series non-ionic surfactants available from Rhodia which are described to be branched isodecyl alcohol ethoxylates. Rhodasurf® DA-530 has been described as having 4 moles of ethoxylation and an HLB of 10.5; Rhodasurf® DA-630 has been described as having 6 moles of ethoxylation with an HLB of 12.5; and Rhodasurf® DA-639 is a 90% solution of DA- 630. Further examples of ethoxylated alcohols include those from Tomah Products (Milton, WI) under the Tomadol® tradename with the formula RO(CH2CH2O)nH where R is the primary linear alcohol and n is the total number of moles of ethylene oxide. The ethoxylated alcohol series from Tomah include 91-2.5; 91-6; 91-8 - where R is linear CyCio/Cn and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; where R is linear Cn and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5 - where R is linear C12/C13 and n is 1, 3, 5, or 6.5; 25-3; 25-7; 25-9; 25-12 - where R is linear C12/C13/C1 / C15 and n is 3, 7, 9, or 12; and 45-7; 45- 13 - where R is linear C1 / C15 and n is 7 or 13. A further class of useful nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C6-C18 alcohols which further include an average of from 2 to 80 moles of ethoxylation per mol of alcohol. These examples include the Genapol® UD (ex. Clariant, Muttenz, Switzerland) described under the tradenames Genapol® UD 030, Cπ-oxo-alcohol polyglycol ether with 3 EO; Genapol® UD, 050 Cπ-oxo-alcohol polyglycol ether with 5 EO; Genapol® UD 070, Cπ- oxo-alcohol polyglycol ether with 7 EO; Genapol® UD 080, Cπ-oxo-alcohol polyglycol ether with 8 EO; Genapol® UD 088, Cn -oxo-alcohol polyglycol ether with 8 EO; and Genapol® UD 110, Cπ-oxo-alcohol polyglycol ether with 11 EO. Exemplary useful nonionic surfactants include the condensation products of a secondary aliphatic alcohols containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are those presently commercially available under the trade name of Tergitol® such as Tergitol 15-S-12 which is described as being Cπ- C15 secondary alkanol condensed with 9 ethylene oxide units, or Tergitol 15-S-9 which is described as being Cπ -C15 secondary alkanol condensed with 12 ethylene oxide units per molecule. A further class of useful nonionic surfactants include those surfactants having a formula: RO(CH2CH20)nH wherein; R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of ethoxy repeating units and is a number of from about 1 to about 12. Surfactants of this formula are presently marketed under the Genapol® tradename (ex. Clariant), which surfactants include the "26-L" series of the general formula RO(CH2CH20)nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from 1 to about 12, such as 26-L-l, 26-L-1.6, 26-L-2, 26-L-3, 26-L-5, 26- L-45, 26-L-50, 26-L-60, 26-L-60N, 26-L-75, 26-L-80, 26-L-98N, and the 24-L .series, derived from synthetic sources and typically contain about 55% C12 and 45% C14 alcohols, such as 24-L-3, 24-L-45, 24-L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N, all sold under the Genapol® tradename. A further class of useful nonionic surfactants include alkoxy block copolymers, and in particular, compounds based on ethoxy/propoxy block copolymers. Polymeric alkylene oxide block copolymers include nonionic surfactants in which the major portion of the molecule is made up of block polymeric C2-C4 alkylene oxides. Such nonionic surfactants, while preferably built up from an alkylene oxide chain starting group, and can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, thiols and secondary alcohols. One group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A):
HO-(EO)x(PO)y(EO)2-H (A)
where EO represents ethylene oxide, PO represents propylene oxide, y equals at least 15, (EO)x+y equals 20 to 50% of the total weight of said compounds, and, the total molecular weight is preferably in the range of about 2000 to 15,000. These surfactants are available under the PLURONIC (ex. BASF) or Emulgen (ex. Kao.) A further group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those can be represented by the formula (B):
R-(EO,PO)a(EO,PO)b-H (B)
wherein R is an alkyl, aryl or aralkyl group, where the R group contains 1 to 20 carbon atoms, the weight percent of EO is within the range of 0 to 45% in one of the blocks a, b, and within the range of 60 to 100% in the other of the blocks a, b, and the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and 5 to 100 moles in the EO rich block. Specific nonionic surfactants which in general are encompassed by Formula B include butoxy derivatives of propylene oxide/ethylene oxide block polymers having molecular weights within the range of about 2000-5000. Still further examples of useful nonionic surfactants include those which can be represented by formula (C) as follows: RO-(BO)n(EO)x-H (C)
wherein EO represents ethylene oxide, BO represents butylene oxide, R is an alkyl group containing I to 20 carbon atoms, n is about 5-15 and x is about 5-15. Yet further useful nonionic surfactants include those which may be represented by the following formula (D): HO-(EO)χ(BO)n(EO)y-H (D)
wherein EO represents ethylene oxide, BO represents butylene oxide, n is about 5-15, preferably about 15, x is about 5-15, preferably about 15, and y is about 5-15, preferably about 15. Still further exemplary useful nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which maybe represented by the following formula:
Figure imgf000009_0001
where (EO) represents ethoxy, (PO) represents propoxy, the amount of (PO)x is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500, and the amount of (EO)y is such as to provide about 20% to 90% of the total weight of said compound. Further useful non-ionic surfactants which may be used in the inventive compositions include those presently marketed under the trade name Pluronics® (ex. BASF). The compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4,000 and preferably 200 to 2,500. The addition of polyoxyethylene radicals of the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble. The molecular weight of the block polymers varies from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight. Preferably, these surfactants are in liquid form and particularly satisfactory surfactants are available as those marketed as Pluronics® L62 and Pluronics® L64. Alkylmonoglycosides and alkylpolyglycosides which find use in the present inventive compositions include known nonionic surfactants which are alkaline and electrolyte stable. Alkylmonoglycosides and alkylpolyglycosides are prepared generally by reacting a monosaccharide, or a compound hydrolyzable to a monosaccharide with an alcohol such as a fatty alcohol in an acid medium. Various glycoside and polyglycoside compounds including alkoxylated glycosides and processes for making them are disclosed in U.S. Pat. Nos. 2,974,134; 3,219,656; 3,598,865; 3,640,998; 3,707,535, 3,772,269; 3,839,318; 3,974,138; 4,223,129 and 4,528,106 the contents of which are incorporated by reference. One exemplary group of such useful alkylpolyglycosides include those according to the formula: R2θ-(CnH2nO)r(Z)x wherein: R2 is a hydrophobic group selected from alkyl groups, alkylphenyl groups, hydroxyalkylphenyl groups as well as mixtures thereof, wherein the alkyl groups may be straight chained or branched, and which contain from about 8 to about 18 carbon atoms, n has a value of 2 - 8, especially a value of 2 or 3; r is an integer from 0 to 10, but is preferably 0, Z is derived from glucose; and, x is a value from about 1 to 8, preferably from about 1.5 to 5. Preferably the alkylpolyglycosides are nonionic fatty alkylpolyglucosides which contain a straight chain or branched chain C8 -C15 alkyl group, and have an average of from about 1 to 5 glucose units per fatty alkylpolyglucoside molecule. More preferably, the nonionic fatty alkylpolyglucosides which contain straight chain or branched C8 -C15 alkyl group, and have an average of from about 1 to about 2 glucose units per fatty alkylpolyglucoside molecule. A further exemplary group of alkyl glycoside surfactants suitable for use in the practice of this invention may be presented by the following formula (A): RO-(R1O)y-(G)x Zb (A) wherein: R is a monovalent organic radical containing from about 6 to about 30, preferably from about 8 to 18 carbon atoms,
Ri is a divalent hydrocarbon radical containing from about 2 to about 4 carbon atoms, y is a number which has an average value from about 0 to about 1 and is preferably 0,
G is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; and, x is a number having an average value from about 1 to 5 (preferably from 1.1 to 2); O II
Z is O2M1, °~C-R2 5 0(CH2), CO2M1, OSO3M1, or ; R2 is (CH2)CO2 M1 or
Figure imgf000011_0002
; (with the proviso that Z can be OzM1 only if Z is in place of a primary hydroxyl group in which the primary hydroxyl-bearing carbon atom, O
CH2OH, is oxidized to form a C— OM1 group b is a number of from 0 to 3x+l preferably an average of from 0.5 to 2 per glycosal group; p is 1 to 10, M1 is H+ or an organic or inorganic counterion, particularly cations such as, for example, an alkali metal cation, ammonium cation, monoethanolamine cation or calcium cation. As defined in Formula (A) above, R is generally the residue of a fatty alcohol having from about 8 to 30 and preferably 8 to 18 carbon atoms. Examples of such alkylglycosides as described above include, for example APG 325 CS Glycoside® which is described as being a 50% C9 -Cπ alkyl polyglycoside, also commonly referred to as D- glucopyranoside, (commercially available from Henkel KGaA) and Glucopon® 625 CS which is described as being a 50% o -C16 alkyl polyglycoside, also commonly referred to as a D-glucopyranoside, (ex. Henkel), well as Glucopon® 225DK, a further alkylpolyglycoside which is more specifically described as being 68 - 72%wt. of alkyl μ(+b) mono- and oligo- C8 -C10 glucopyranosides (ex. Henkel) which is derived from glucose derivatives of maize, and fatty alcohols derived from coconut and palm kern oils. Further commercially available examples of suitable alkyl polyglycosides having differing carbon chain lengths include those currently marketed under the tradename Glucopon 220, Glucopon 225, Glucopon 425, Glucopon 600, and Glucopon 625, all available from Henkel Corporation Further nonionic surfactants which may be included in the inventive compositions include alkoxylated alkanolamides, preferably C8-C24 alkyl di(C -C3 alkanol amides), as represented by the following formula: R5-CO-NH-R6-OH wherein R5 is a branched or straight chain Cs-C24 alkyl radical, preferably a Cio-Ciβ alkyl radical and more preferably a C12-C1 alkyl radical, and Re is a C1-C4 alkyl radical, preferably an ethyl radical. According to certain particularly preferred embodiments the detersive surfactant constituent necessarily comprises a nonionic surfactant based on a linear primary alcohol ethoxylate particularly wherein the alkyl portion is a C8 to C16, but particularly a C9 to Cπ alkyl group, and having an average of between about 6 to about 8 moles of ethoxylation. The detersive surfactant constituent according to the invention desirably includes at least one anionic surfactant and/or anionic soap surfactant in conjunction with at least one nonionic surfactant, particularly a nonionic surfactant derived from alcohol alkoxylates. The detersive surfactant constituent of the present invention comprises from about 0.1 to about 30 wt%, preferably from about 1 to about 20 wt%, and more preferably from about 2 to about 10 wt% of the dilutable hard surface cleaning composition of which they form a part. The dilutable hard surface cleaning compositions of the invention necessarily include at least one thickener constituent. Thickeners useful in the present invention to achieve this viscosity are selected from the group consisting of polysaccharide polymers selected from cellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses, carboxy alkyl hydroxy alkyl celluloses, naturally occurring polysaccharide polymers such as xanthan gum, guar gum, locust bean gum, tragacanth gum, or derivatives thereof, polycarboxylate polymers, polyacrylamides, clays, and mixtures thereof. Examples of the cellulose derivatives include methyl cellulose ethyl cellulose, hydroxymethyl cellulose hydroxy ethyl cellulose, hydroxy propyl cellulose, carboxy methyl cellulose, carboxy methyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy propyl methyl cellulose, ethylhydroxymethyl cellulose and ethyl hydroxy ethyl cellulose. Exemplary polycarboxylate polymers thickeners have a molecular weight from about 500,000 to about 4,000,000, preferably from about 1,000,000 to about 4,000,000, with, preferably, from about 0.5% to about 4% crosslinking. Preferred polycarboxylate polymers include polyacrylate polymers including those sold under trade names Carbopol®, Acrysol® ICS-1 and Sokalan®. The preferred polymers are polyacrylates. Other monomers besides acrylic acid can be used to form these polymers including such monomers as ethylene and propylene which act as diluents, and maleic anhydride which acts as a source of additional carboxylic groups. The polycarboxylate polymer can be a non-associative thickener or stabilizer, such as a homopolymer or a copolymer of an olefinically unsaturated carboxylic acid or anhydride monomers containing at least one activated carbon to carbon olefinic double bond and at least one carboxyl group or an alkali soluble acrylic emulsion, or an associative thickener or stabilizer, such as a hydrophobically modified alkali soluble acrylic emulsion or a hydrophobically modified nonionic polyol polymer, i.e., a hydrophobically modified urethane polymer, or combinations thereof. The copolymers are preferably of a polycarboxylic acid monomer and a hydrophobic monomer. The preferred carboxylic acid is acrylic acid. The homopolymers and copolymers preferably are crosslinked. Homopolymers of polyacrylic acid are described, for example, in U.S. Pat. No. 2,798,053. Examples of homopolymers which are useful include Carbopol® 934, 940, 941, Ultrez 10, ETD 2050, and 974P polymers, which are available from Noveon. Such polymers are homopolymers of unsaturated, polymerizable carboxylic monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, and the like. Hydrophobically modified polyacrylic acid polymers are described, for example, in U.S. Pat. Nos. 3,915,921, 4,421,902, 4,509,949, 4,923,940, 4,996,274, 5,004,598, and 5,349,030. These polymers have a large water-loving hydrophilic portion (the polyacrylic acid portion) and a smaller oil-loving hydrophobic portion (which can be derived from a long carbon chain acrylate ester). Representative higher alkyl acrylic esters are decycl acrylate, lauryl acrylate, stearyl acrylate, behenyl acrylate and melissyl acrylate, and the corresponding methacrylates. It should be understood that more than one carboxylic monomer and more than one acrylate ester or vinyl ester or ether or styrenic can be used in the monomer charge. The polymers can be dispersed in water and neutralized with base to thicken the aqueous composition, form a gel, or emulsify or suspend a deliverable. Useful polymers are sold as Carbopol® 1342 and 1382 and Pemulen® TR-1, TR-2, 1621, and 1622, all available from Noveon. The carboxyl containing polymers are prepared from monomers containing at least one activated vinyl group and a carboxyl group, and would include copolymers of polymerizable carboxylic monomers with acrylate esters, acrylamides, alkylated acrylamides, olefins, vinyl esters, vinyl ethers, or styrenics. The carboxyl containing polymers have molecular weights greater than about 500 to as high as several billion, or more, usually greater than about 10,000 to 900,000 or more. Also useful are inte olymers of hydrophobically modified monomers and steric stabilizing polymeric surface active agents having at least one hydrophilic moiety and at least one hydrophobic moiety or a linear block or random comb configuration or mixtures thereof. Examples of steric stabilizers which can be used are Hypermer®, which is a poly(12-hydroxystearic acid) polymer, available from Imperial Chemical Industries Inc. and Pecosil®, which is a mefhyl-3-polyethoxypropyl siloxane-ω-phosphate polymer, available from Phoenix Chemical, Somerville, N.J. These are taught by U.S. Pat. Nos. 4,203,877 and 5,349,030, the disclosures of which are incorporated herein by reference. The polymers can be crosslinked in a manner known in the art by including, in the monomer charge, a suitable crosslinker in amount of about 0.1 to 4%, preferably 0.2 to 1% by weight based on the combined weight of the carboxylic monomer and the comonomer(s). The crosslinker is selected from polymerizable monomers which contain a polymerizable vinyl group and at least one other polymerizable group. Polymerization of the carboxyl-containing monomers is usually carried out in a catalyzed, free radical polymerization process, usually in inert diluents, as is known in the art. Other polycarboxylic acid polymer compositions which can be employed include, for example, crosslinked copolymers of acrylates, (meth)acrylic acid, maleic anhydride, and various combinations thereof. Commercial polymers are available from Rheox Inc., Highstown, N.J. (such as Rheolate® 5000 polymer), 3 V Sigma, Bergamo, Italy (such as Stabelyn® 30 polymer, which is an acrylic acid/vinyl ester copolymer, or Poly gel® and Synthalen® polymers, which are crosslinked acrylic acid polymers and copolymers), Noveon (such as Carbopol 674 (lightly crosslinked polyacrylate polymer), Carbopol 676 (highly crosslinked polyacrylate polymer), Carbopol EP-1 thickener, which is a acrylic emulsion thickener), or Rohm and Haas (such as Acrysol® ICS-1 and Aculyn® 22 thickeners, which are hydrophobically modified alkali-soluble acrylic polymer emulsions and Aculyn® 44 thickener, which is a hydrophobically modified nonionic polyol). Preferred are the Carbopol® and Pemulen® polymers, generally. The choice of the specific polymer to be employed will depend upon the desired rheology of the composition, and the identity of other compositional ingredients. Clay thickeners comprise, for example, colloid-forming clays, for example, such as smectite and/or attapulgite types. The clay materials can be described as expandable layered clays, i.e., aluminosilicates and magnesium silicates. The term "expandable" as used to describe the instant clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The expandable clays used herein are those materials classified geologically as smectites (or montmorillonite) and attapulgites (or polygorskites). Smectites are three-layered clays. There are two distinct classes of smectite-type clays. In the first, aluminum oxide is present in the silicate crystal lattice; in the second class of smectites, magnesium oxide is present in the silicate crystal lattice. The general formulas of these smectites are Al (Si2O5)2(OH)2 and Mg3(Si2O5)(OH)2, for the aluminum and magnesium oxide type clays, respectively. It is to be recognized that the range of the water of hydration in the above formulas may vary with the processing to which the clay has been subjected. Commercially available clays include, for example, montmorillonite, bentonite, volchonskoite, nontronite, beidellite, hectorite, saponite, sauconite and vermiculite. The clays herein are available under various trade names such as Gelwhite GP, Gelwhite H, Mineral Colloid BP, and Laponite from Southern Clay Products, Inc., Texas; and Van Gel O from R. T. Vanderbilt. Gelwhite H-NF has a typical chemical analysis of SiO2 66.5%; Al2O3 14.7%; MgO 3.2%; Fe2O3 0.8%; CaO 2.2%; Na2O 3.3%; K2O 0.1%; TiO2 0.2%. Gelwhite L-NF has a typical chemical analysis of SiO2 66.5%; Al2O3 14.7%; MgO .3.2%; Fe2O3 0.8%; CaO 2.2%; Na2O 3.3%; K2O 0.1%; TiO2 0.2%. Gelwhite GP has a typical chemical analysis of SiO2 66.5%; Al2O3 14.7%; MgO 3.2%; Fe2O3 0.8%; CaO 2.2%; Na2O 3.3%; K2O 0.1%; TiO2 0.2%. Mineral Colloid BP has a typical chemical analysis of Si0262.9%; Al2O3 17.1%; MgO 2.4%; Fe2O34.8%; CaO 0.7%; Na2O 2.1%; K2O 0.2%; TiO2 0.1%. A second type of expandable clay material useful in the instant invention is classified geologically as attapulgite (polygorskite). Attapulgites are magnesium-rich clays having principles of superposition of tetrahedral and octahedral unit cell elements different from the smectites. A typical attapulgite analyses yields 55.02% SiO2; 10.24% Al2O3; 3.53% Fe2O3; 10.45% MgO; 0.47% K2O; 9.73% H2O removed at 150°C; 10.13% H O removed at higher temperatures. Like the smectites, attapulgite clays are commercially available. For example, such clays are marketed under the tradename Attagel, i.e. Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals & Chemicals Corporation. The preferred clay thickeners comprise the inorganic, colloid forming clays of smectite and/or attapulgite types. Preferred clays include products from Vanderbilt Chemical Company such as VanGel O. The amount of thickener used in the present invention can range from about 0.1 to
10 wt%. The ultimate viscosity of the inventive compositions is largely due to the selection of the thickening constituent. The inventive compositions exhibit a viscosity greater than that of water, and desirably exhibit a viscosity of at least about 50 cps. More preferably the inventive compositions exhibit a viscosity of from about 50 cps to about 2000 cps, but most preferably exhibit a viscosity of between about 300 cps and 700 cps, and most particularly of about 500 cps. The inventors have found that the inventive compositions need be maintained in a thickened state in order to provide sufficient suspension of the at least one opacifying agent present. The dilutable hard surface cleaning compositions of the invention necessarily include at least one opacifying constituent. Such materials are typically either polymers, oleochemical fatty dispersions or minerals such as mica. Exemplary useful and preferred materials include alkylene glycol mono- and di-stearates particularly Ci-Cβ glycol mono- and di-stearates, especially ethylene glycol monostearate, ethylene glycol distearate and propylene glycol monostearate, presently commercially available as Sipoest® materials, glycerol mono- and di-stearate. Further useful materials which may be used to impart an opacifying and pearlescent appearance to the inventive compositions are those presently commercially available as Euperlan® materials. Such include Euperlan® PK 771 and Euperlan® PK 810 both described to be a mixture of sodium laureth sulfate, glycol distearate, cocoamine monoethanolamine and laureth-10; Euperlan® PK 900 described to be a mixture of PEG-3 distearate and sodium laureth sulfate; Euperlan® PK 1200 described to be a mixture of coco-glucoside, glycol distearate and glycerin; Euperlan® PK 3000 and Euperlan® PK 4000 both described to be a mixture of glycol distearate, laureth-4 and cocoamidopropyl betaine. These Euperlan® materials are preferred as they provide not only an opacifying effect but also provide for a pearlescent appearance to the final product which is highly desirable. The specific opacifying constituent should be selected to be compatible with the detersive surfactant constituent. Typically the amount of the opacifying constituent used in the present invention can range from about 0.1 to 10 wt%. While optional, in preferred embodiments the present inventive compositions comprise one or more water soluble or water dispersible organic solvents. Exemplarly useful water soluble organic solvents include short chain -Ce alcohols, glycol ethers, and mixtures thereof. Such water soluble organic solvents provide effective solubilization of many types of greases and fats which may be encountered in soils on hard surfaces. Of course two or more organic solvents may be used as the organic solvent constituent according to the invention. Examples of short chain alcohols include ethanol, propanol, and isopropanol. Examples of such useful glycol ethers include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, diethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, and mixtures thereof. The glycol ethers are preferred, and particularly preferred are compositions wherein the organic solvent constituent is solely one or more glycol ethers. The water soluble organic solvent constituent may be present in the inventive compositions in amounts of from about 0.1 to about 20 wt%, preferably in amounts of from about 0.5 to about 10 wt%. The compositions of the present invention can also optionally comprise one or more further constituents which are directed to improving the aesthetic or functional features of the inventive compositions. By way of non-limiting example such further constituents include one or more coloring agents, fragrances and fragrance solubilizers, other surfactants, pH adjusting agents and pH buffers including organic and inorganic salts, optical brighteners, hydrotropes, antifoaming agents, anti-oxidants, AND preservatives. When one or more of the optional constituents is added, i.e., fragrance and/or coloring agents, the esthetic and consumer appeal of the product is often favorably improved. The use and selection of these optional constituents is well known to those of ordinary skill in the art. When present, the one or more optional constituents present in the inventive compositions do not exceed about 10%wt, preferably do not exceed 5%wt. The compositions according to the invention optionally but desirably include an amount of a pH adjusting agent or pH buffer composition. Such compositions include many which are known to the art and which are conventionally used. By way of non- limiting example pH adjusting agents include phosphorus containing compounds, monovalent and polyvalent salts such as of silicates, carbonates, and borates, certain acids and bases, tartrates and certain acetates. Further exemplary pH adjusting agents include mineral acids, basic compositions, and organic acids, which are typically required in only minor amounts. By way of further non-limiting example pH buffering compositions include the alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates, bicarbonates, polycarbonateshydroxides, and mixtures of the same. Certain salts, such as the alkaline earth phosphates, carbonates, hydroxides, can also function as buffers. It may also be suitable to use as buffers such materials as aluminosilicates (zeolites), borates, aluminates and certain organic materials such as gluconates, succinates, maleates, and their alkali metal salts. Desirably the compositions according to the invention include an effective amount of an organic acid and/or an inorganic salt form thereof which may be used to adjust and maintain the pH of the compositions of the invention to the desired pH range. Particularly useful is are carbonates and bicarbonates and particularly and metal salts thereof such as sodium carbonate, sodium bicarbonate which are widely available and which are effective in providing pH adjustment and buffering effects. Preferably the pH of the inventive compositions are alkaline, desirably in excess of 7, more desirably the pH of the compositions are 8 or greater, still more preferably are about 9 or greater. Further optional, but advantageously included constituents are one or more coloring agents which find use in modifying the appearance of the compositions and enhance their appearance from the perspective of a consumer or other end user. Known coloring agents may be incorporated in the compositions in any effective amount to improve or impart to compositions a desired appearance or color. Such a coloring agent or coloring agents may be added in a conventional fashion, i.e., admixing to a composition or blending with other constituents used to form a composition. Such coloring agent may be based on naturally occurring coloring agents, or may be based on one or more synthetically produced materials including synthetic dyes and pigments particularly those recited in the Color Index. Further optional, but desirable constituent include fragrances, natural or synthetically produced. Such fragrances may be added in any conventional manner, admixing to a composition or blending with other constituents used to form a composition, in amounts which are found to be useful to enhance or impart the desired scent characteristic to the composition, and/or to cleaning compositions formed therefrom. Exemplary useful fragrances include those based on digeranyl succinate, dineryl succinate, geranyl neryl succinate, geranyl phenylacetate, neryl phenylacetate, geranyl laurate, neryl laurate, di(b-citronellyl) maleate, dinonadol maleate, diphenoxyanol maleate, di(3,7-dimethyl-l-octanyl) succinate, di(cyclohexylethyl) maleate, diflralyl succinate, di(phenylethyl) adipate, 7-acetyl-l,2,3,4,5,6,7,8-octahydro- 1,1,6,7-tetramethyl naphthalene, ionone methyl, ionone gamma methyl, methyl cedrylone, methyl dihydrojasmonate, methyl l,6,10-trimethyl-2,5,9-cyclododecatrien-l- yl ketone, 7-acetyl-l,l,3,4,4,6-hexamethyl tetralin, 4-acetyl-6-tert-butyl-l- ,1 -dimethyl indane, para-hydroxy-phenyl-butanone, benzophenone, methyl beta-naphfhyl ketone, 6- acetyl-l,l,2,3,3,5hexamethyl indane, 5-acetyl-3-isopropyl-l,l,2,6-tetramethyl indane, 1- dodecanal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-l-carboxaldehyde, 7-hydroxy- 3,7-dimethyl ocatanal, 10-undecen-l-al, isohexenyl cyclohexyl carboxaldehyde, formyl tricyclodecane, condensation products of hydroxycitronellal and methyl anthranilate, condensation products of hydroxycitronellal and indol, condensation products of phenyl acetaldehyde and indol, 2-methyl-3-(para-tert-butylphenyl)-propionaldehyd- e, ethyl vanillin, heliotropin, hexyl cinnamic aldehyde, amyl cinnamic aldehyde, 2-methyl-2- (para-iso-propylphenyl)propionaldehyde, coumarin, decalactone gamma, cyclopentadecanolide, 16-hydroxy-9-hexadecenoic acid lactone, 1,3,4,6,7,8-hexahydro- 4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-b- enzopyrane, beta-naphthol methyl ether, ambroxane, dodecahydro-3a,6,6,9a-t- eframethyinaphtho[2,lb]furan, cedrol, 5-(2,2,3- trimethylcyclopent-3-enyl)~ 3-methylpentan-2-ol, 2-ethyl-4-(2,2,3-trimethyl-3- cyclopenten-l-yl)-2-bute- n-l-ol, caryophyllene alcohol, tricyclodecenyl propionate, tricyclodecenyl acetate, benzyl salicylate, cedryl acetate, para-(tert-butyι) cyclohexyl acetate, essential oils, resinoids, and resins from a variety of sources including but not limited to orange oil, lemon oil, patchouli, Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander, lavandin, and lavender, phenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2-(l,l- dimethylethyl)cyclohexanol acetate, benzyl acetate, orange terpenes, eugenol, diethylphthalate, and combinations thereof. The fragrance constituent may also be based on one or more essential oils including one or more selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Canaga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69°C (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun balsam, Heliotropin, Isobornyl acetate, Isolongifolene, Juniper berry oil, L-methhyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol crystals, Methyl cedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), Wintergreen. Other fragrance compounds not particularly eludicated here but which are found useful in providing a desirable fragrancing effect may also be included in the inventive compositions. When present, the fragrance constituent maybe included in any effective amount, and of course mixtures of two or more fragrance compounds may be used to provide the fragrance constituent. Desirably the fragrance constituent in present in an amount not exceeding 5%wt. of the inventive composition of which it forms a part, and more preferably is present in an amount not exceeding 1 %wt. In compositions which include a fragrance, it is frequently desirable to include a fragrance solubilizer which assists in the dispersion, solution or mixing of the fragrance constituent in an aqueous base. These include known art compounds, including condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C1o-C2o alkanoic acid known to be useful as nonionic surfactants. Further examples of such suitable surfactants include water soluble nonionic surfactants of which many are commercially known and by way of non-limiting example include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates on primary alkanols, and condensates of ethylene oxide with sorbitan fatty acid esters.. This fragrance solubilizer component is added in minor amounts, particularly amount which are found effective in aiding in the solubilization of the fragrance component, but not in any significantly greater proportion, such that it would be considered as a surfactant constituent. Such minor amounts of fragrance solubilizer recited herein is generally up to about 0.2% by weight of the fragrance constituent in the inventive compositions but is more generally an amount of about 0.1%) by weight and less, and preferably is present in amounts of about 0.05% by weight and less. The inventive compositions optionally but desirably comprise a preservative constituent. Since a significant portion of the inventive compositions comprise water, it is preferably that the preservative be water soluble. Desirably, the selected water soluble preservatives are those which exhibit stability and efficacy in the aqueous compositions according to the invention at neutral, but preferably at alkaline pH's especially in the preferred pH ranges noted above. Such water soluble preservatives include compositions which include parabens, including methyl parabens and ethyl parabens, glutaraldehyde, formaldehyde, 2-bromo-2-nitropropoane-l,3-diol, 5-chloro-2-methyl-4-isothiazolin-3- one, 2-methyl-4-isothiazoline-3-one, and mixtures thereof. One exemplary composition is a combination 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3- one where the amount of either component may be present in the mixture anywhere from 0.001 to 99.99 weight percent, based on the total amount of the preservative. For reasons of availability, the most preferred preservative are those commercially available preservative comprising a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2- methyl-4-isothiazolin-3-one marketed under the trademark KATHON® CG ICP as a preservative composition presently commercially available from Rohm and Haas (Philadelphia, PA). Further useful preservative compositions include KATHON® CG/ICP II, a further preservative composition presently commercially available from Rohm and Haas (Philadelphia, PA), PROXEL® which is presently commercially available from Zeneca Biocides (Wilmington, DE), SUTTOCIDE® A which is presently commercially available from Sutton Laboratories (Chatam, NJ) as well as TEXTAMER® 38 AD which is presently commercially available from Calgon Corp. (Pittsburgh, PA). Particularly preferred for use in the inventive composition is a preparation containing 1,3- dihydroxymethyl-5,5-dimethylhydantoin and 3-iodo-2-propynyl butyl carbamate which is presently commercially available as Dantogard® Plus Liquid from Lonza Corp. (Fairlawn, NJ.) When included, the preservative constituent is present in the dilutable hard surface cleaning compositions of the present invention in any amount which is effective in retarding or eliminating the growth of undesired microorganisms in the inventive compositions particularly upon standing. The preservative constituent need be present in only minor amounts, and is advantageously present in amounts for from about 0.001%wt. to about 0.5%) wt, more preferably is present in an amount of from about 0.01 - 0.1%wt. In preferred embodiments of the invention the preservative constituent is necessarily present. As the concentrate compositions are aqueous, water forms a major constituent. Water is added in order to provide 100 wt% of the concentrate composition. The water may be tap water, but is preferably distilled and/or deionized water. If the water is tap water, it is preferably appropriately filtered in order to remove any undesirable impurities such as organics or inorganics, especially mineral salts which are present in hard water which may thus interfere with the operation of the other constituents of the invention, as well as any other optional components of the liquid concentrates according to the invention. The compositions according to the invention are useful in the cleaning of surfaces, especially hard surfaces in need of such treatment. In accordance with the present inventive process, cleaning of such surfaces comprises the step of applying a stain releasing effective amount of a composition as taught herein to such a stained surface. Afterwards, the compositions are optionally but desirably wiped, scrubbed or otherwise physically contacted with the hard surface, and further optionally, may be subsequently rinsed from such a cleaned hard surface. While the inventive compositions described herein may be provided as a ready to use product which may be directly applied to a hard surface, it is desirably provided in a concentrated form intended to be diluted in water to form a cleaning composition therefrom. What is to be understood by the term "concentrate" and "concentrate composition" in this specification and claims is the pre-consumer dilution and composition of the cleaning composition which is the essentially the form of the product prepared for sale to the consumer or other end user with required product shelf life. Such a consumer or other end user would then normally be expected to dilute the same with water to form a cleaning composition. It is to be understood however that nothing in this invention would bar its use as cleaning composition without any further dilution and it may be used in the concentrations in which it was prepared for sale. Similarly, what is to be understood by the term "cleaning compositions" are the water diluted compositions which are expected to be prepared by the consumer or other end user by mixing a measured amount of the "concentrate" with water in order to form an appropriately diluted cleaning composition which is suitable for use in cleaning applications, especially in the cleaning of hard surfaces. It is also to be understood, that proportions of one or more constituents have been and generally are referred to as percent by weight or as parts by weight based on a measure of 100% by weight, unless otherwise indicated. As generally denoted above, the formulations according to the invention include both cleaning compositions and concentrates as outlined above which differ only in the relative proportion of water to that of the other constituents forming such formulations. While the concentrated form of the cleaning compositions find use in their original form, they are more frequently used in the formation of a cleaning composition therefrom. Such may be easily prepared by diluting measured amounts of the concentrate compositions in water by the consumer or other end user in certain weight ratios of concentrate:water, and optionally, agitating the same to ensure even distribution of the concentrate in the water. As noted, the concentrate may be used without dilution, i.e., in concentrate:water concentrations of 1:0, to extremely dilute dilutions such as 1:200. Desirably, the concentrate is diluted in the range of 1:0.1-1:100, preferably in the range of 1:10-1:50. The actual dilution selected is in part determinable by the degree and amount of dirt and grime to be removed from a surface(s), the amount of mechanical force imparted to remove the same, as well as the observed efficacy of a particular dilution. Generally better results and faster removal is to be expected at lower relative dilutions of the concentrate in water. The following examples illustrate an exemplary formulation of the invention and particular preferred embodiments of the inventive compositions. The terms "parts by weight" or "percentage weight" as well as "%wt." are used interchangeably in the specification and in the following Examples wherein the weight percentages of each of the individual constituents are indicated in weight percent based on the total weight of the composition, unless indicated otherwise.
Example Preparation of Example Formulations: Exemplary formulations illustrating certain preferred embodiments of the inventive compositions and described in more detail in Table 1 below were formulated generally in accordance with the following protocol. These constituents were used "as is" from their respective supplier. Into a suitably sized vessel, a measured amount of water was provided after which the constituents were added in no specific or uniform sequence, which indicated that the order of addition of the constituents was not critical. All of the constituents were supplied at room temperature, and any remaining amount of water was added thereafter. Mixing of the constituents was achieved by the use of a mechanical stirrer with a small diameter propeller at the end of its rotating shaft. Mixing, which generally lasted from 5 minutes to 120 minutes was maintained until the particular exemplary formulation appeared to be homogeneous. The exemplary compositions were readily pourable, and retained well mixed characteristics (i.e., stable mixtures) upon standing for extend periods. The compositions of the example formulations are listed on Table 1.
Figure imgf000025_0001
As is indicated, to all of the formulations of Table 1 was added sufficient deionized water in "quantum sufficient" to provide 100 parts by weight of a particular formulation. The identity of the constituents of Table 1 above are described in more detail on Table 2, below, including the "actives" percentage of each were a constituent was not provided by its supplier as 100%wt. "actives".
Figure imgf000026_0001
The composition according to Example 1 provided good cleaning of hard surfaces when used without further dilution, as well as when diluted in further ratios of composition:water of 1:20 and 1:50 . While the invention is susceptible of various modifications and alternative forms, it is to be understood that specific embodiments thereof have been shown by way of example in the drawings which are not intended to limit the invention to the particular forms disclosed; on the contrary the intention is to cover all modifications, equivalents and alternatives falling within the scope and spirit of the invention as expressed in the appended claims.

Claims

Claims:
1. Aqueous, dilutable hard surface cleaning compositions which comprise: one or more detersive surfactants, preferably containing one or more anionic surfactants including anionic soaps optionally but preferably in conjunction with one or more nonionic surfactants; one or more thickener constituents; one or more opacifying constituents; optionally but desirably one or more organic solvents; optionally one or more constituents for improving the aesthetic or functional features of the inventive compositions; and, water.
2. The composition according to claim 1 which comprises an anionic soap.
3. The composition according to claim 1 which comprises an nonionic surfactant.
4. The composition according to claim 4 which comprises a linear alcohol ethoxylated surfactant.
5. The composition according to any preceding claim which comprises a sulfonate based anionic surfactant.
6. The composition according to any preceding claim which comprises an opacifiving constituent selected from one or more of: mixtures of sodium laureth sulfate, glycol distearate, cocoamine monoethanolamine and laureth- 10; mixtures of PEG-3 distearate and sodium laureth sulfate; mixtures of coco-glucoside, glycol distearate and glycerin; and, mixtures of glycol distearate, laureth-4 and cocoamidopropyl betaine.
7. The composition according to any preceding claim wherein the composition exhibits a viscosity of at least about 50 cps.
8. The composition according to claim 7 wherein the composition exhibits a viscosity from about 50 cps to about 2000 cps.
9. A composition of claim 1 substantially as described with reference to the Example.
PCT/GB2004/004798 2003-11-14 2004-11-15 Cleaning compositions WO2005049783A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
BRPI0415057-0A BRPI0415057A (en) 2003-11-14 2004-11-15 cleaning compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0326505.5 2003-11-14
GB0326505A GB2408051A (en) 2003-11-14 2003-11-14 Hard surface cleaning compositions

Publications (1)

Publication Number Publication Date
WO2005049783A1 true WO2005049783A1 (en) 2005-06-02

Family

ID=29726497

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2004/004798 WO2005049783A1 (en) 2003-11-14 2004-11-15 Cleaning compositions

Country Status (3)

Country Link
BR (1) BRPI0415057A (en)
GB (1) GB2408051A (en)
WO (1) WO2005049783A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8143206B2 (en) 2008-02-21 2012-03-27 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US8143205B2 (en) 2008-02-21 2012-03-27 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US8980813B2 (en) 2008-02-21 2015-03-17 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits
US9169456B2 (en) 2008-02-21 2015-10-27 S.C. Johnson & Son, Inc. Cleaning composition comprising an ethoxylated alcohol blend, having high self-adhesion and providing residual benefits
US9410111B2 (en) 2008-02-21 2016-08-09 S.C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US9481854B2 (en) 2008-02-21 2016-11-01 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3326807A (en) * 1963-02-15 1967-06-20 Ici Ltd Detergent compositions
GB2234981A (en) * 1989-08-02 1991-02-20 Parknotts Limited Liquid laundry detergent
WO1991008282A1 (en) * 1989-11-24 1991-06-13 Unilever N.V. Cleaning composition
US5246613A (en) * 1990-07-20 1993-09-21 The Procter & Gamble Company Aqueous isotropic personal liquid cleansing composition with triethanol amine soap, selected electrolyte and synthetic surfacant
US5346641A (en) * 1992-01-17 1994-09-13 The Clorox Company Thickened aqueous abrasive cleanser with improved colloidal stability
WO1995004807A1 (en) * 1993-08-10 1995-02-16 The Procter & Gamble Company Dishwashing detergent comprising a secondary soap and lipase enzyme
US5736503A (en) * 1992-11-30 1998-04-07 The Procter & Gamble Company High sudsing detergent compositions with specially selected soaps
DE10216509A1 (en) * 2002-04-11 2003-10-23 Beiersdorf Ag Free-flowing cosmetic or dermatological cleansing gel contains 12-22C fatty acid as alkali(ne earth) soap together with pre-gelatinized crosslinked starch derivative

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2362114C2 (en) * 1973-12-14 1984-07-05 Henkel KGaA, 4000 Düsseldorf Liquid foam-regulated detergent and cleaning agent
GB1534680A (en) * 1977-10-14 1978-12-06 Colgate Palmolive Co Cleaning compositions
EP0040882B1 (en) * 1980-05-27 1985-01-30 THE PROCTER & GAMBLE COMPANY Liquid detergent compositions
GB8325541D0 (en) * 1983-09-23 1983-10-26 Unilever Plc Liquid thickened bleaching composition
GB8328991D0 (en) * 1983-10-31 1983-11-30 Unilever Plc Liquid scouring compositions
GB2322379A (en) * 1997-02-24 1998-08-26 Reckitt & Colman South Africa Abrasive bleach containing composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3326807A (en) * 1963-02-15 1967-06-20 Ici Ltd Detergent compositions
GB2234981A (en) * 1989-08-02 1991-02-20 Parknotts Limited Liquid laundry detergent
WO1991008282A1 (en) * 1989-11-24 1991-06-13 Unilever N.V. Cleaning composition
US5246613A (en) * 1990-07-20 1993-09-21 The Procter & Gamble Company Aqueous isotropic personal liquid cleansing composition with triethanol amine soap, selected electrolyte and synthetic surfacant
US5346641A (en) * 1992-01-17 1994-09-13 The Clorox Company Thickened aqueous abrasive cleanser with improved colloidal stability
US5736503A (en) * 1992-11-30 1998-04-07 The Procter & Gamble Company High sudsing detergent compositions with specially selected soaps
WO1995004807A1 (en) * 1993-08-10 1995-02-16 The Procter & Gamble Company Dishwashing detergent comprising a secondary soap and lipase enzyme
DE10216509A1 (en) * 2002-04-11 2003-10-23 Beiersdorf Ag Free-flowing cosmetic or dermatological cleansing gel contains 12-22C fatty acid as alkali(ne earth) soap together with pre-gelatinized crosslinked starch derivative

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8143206B2 (en) 2008-02-21 2012-03-27 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US8143205B2 (en) 2008-02-21 2012-03-27 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US8980813B2 (en) 2008-02-21 2015-03-17 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits
US9169456B2 (en) 2008-02-21 2015-10-27 S.C. Johnson & Son, Inc. Cleaning composition comprising an ethoxylated alcohol blend, having high self-adhesion and providing residual benefits
US9175248B2 (en) 2008-02-21 2015-11-03 S.C. Johnson & Son, Inc. Non-ionic surfactant-based cleaning composition having high self-adhesion and providing residual benefits
US9181515B2 (en) 2008-02-21 2015-11-10 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US9243214B1 (en) 2008-02-21 2016-01-26 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US9296980B2 (en) 2008-02-21 2016-03-29 S.C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US9399752B2 (en) 2008-02-21 2016-07-26 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US9410111B2 (en) 2008-02-21 2016-08-09 S.C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US9481854B2 (en) 2008-02-21 2016-11-01 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US9771544B2 (en) 2008-02-21 2017-09-26 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits
US9982224B2 (en) 2008-02-21 2018-05-29 S. C. Johnson & Son, Inc. Cleaning composition having high self-adhesion and providing residual benefits comprising a cationic/nonionic surfactant system
US10266798B2 (en) 2008-02-21 2019-04-23 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits
US10392583B2 (en) 2008-02-21 2019-08-27 S. C. Johnson & Son, Inc. Cleaning composition with a hydrophilic polymer having high self-adhesion and providing residual benefits
US10435656B2 (en) 2008-02-21 2019-10-08 S. C. Johnson & Son, Inc. Cleaning composition comprising a fatty alcohol mixture having high self-adhesion and providing residual benefits
US10597617B2 (en) 2008-02-21 2020-03-24 S. C. Johnson & Son, Inc. Cleaning composition that provides residual benefits

Also Published As

Publication number Publication date
GB0326505D0 (en) 2003-12-17
GB2408051A (en) 2005-05-18
BRPI0415057A (en) 2006-11-28

Similar Documents

Publication Publication Date Title
EP1948769B1 (en) Improved hard surface cleaning compositions
AU2008324018B2 (en) Aqueous acidic hard surface cleaning and disinfecting compositions
US7196046B2 (en) Hard surface cleaner comprising a suspension of alginate beads
US8173585B2 (en) Acidic hard surface cleaning compositions
US8729005B2 (en) Hard surface cleaning compositions
US10435650B2 (en) Cleaning composition and method for using the same
EP1994129B1 (en) Aqueous highly acidic hard surface cleaning compositions
MX2007015393A (en) Light-duty dishwashing detergent compositions.
GB2427614A (en) Dishwashing detergent composition
US20050272622A1 (en) Thickened abrasive cleaner
EP1963472B1 (en) Improvements in or relating to organic compositions
AU1235800A (en) Liquid crystal compositions containing a 2-alkyl alkanol and abrasive
WO2005049783A1 (en) Cleaning compositions
WO2007099294A1 (en) Hard surface cleaning composition
EP1456341A1 (en) Liquid cleaning composition having an improved preservative system

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: PI0415057

Country of ref document: BR

122 Ep: pct application non-entry in european phase