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US20040194800A1 - Use of sulfonated polystyrene polymers in hard surface cleaners to provide easier cleaning benefit - Google Patents

Use of sulfonated polystyrene polymers in hard surface cleaners to provide easier cleaning benefit Download PDF

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Publication number
US20040194800A1
US20040194800A1 US10/796,663 US79666304A US2004194800A1 US 20040194800 A1 US20040194800 A1 US 20040194800A1 US 79666304 A US79666304 A US 79666304A US 2004194800 A1 US2004194800 A1 US 2004194800A1
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poly
composition
styrenesulfonate
sodium
hard surface
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US10/796,663
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Jeanne Chang
Natalie Cadena
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Solvay USA Inc
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Individual
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Priority to JP2006509179A priority Critical patent/JP2007525549A/en
Priority to CA002517859A priority patent/CA2517859A1/en
Priority to EP04718017A priority patent/EP1603998A4/en
Priority to BRPI0408109-9A priority patent/BRPI0408109A/en
Priority to US10/796,663 priority patent/US20040194800A1/en
Priority to PCT/US2004/006798 priority patent/WO2004092316A1/en
Assigned to RHODIA INC. reassignment RHODIA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHANG, JEANNE, CADENA, NATALIE
Publication of US20040194800A1 publication Critical patent/US20040194800A1/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • This invention relates to the use of sulfonated polystyrene polymers in hard surface cleaners.
  • Hard surface cleaners typically contain nonionic surfactants, an anti-bacterial agent (which may be a quaternary ammonium type surfactant), chelating agents, a solvent, and water.
  • an anti-bacterial agent which may be a quaternary ammonium type surfactant
  • anionic surfactants may be used in which case the anti-bacterial agent may be excluded or replaced by something other than a quaternary ammonium-type surfactant.
  • the most common surfactant systems for household cleaners are alkyl polyglucosides, or alkyl ethoxylates.
  • Hard surface cleaners are formulated so as to provide cleaning benefit, with little or no foam, and very fast drying so as to leave little or no streaking or residue.
  • the surfactants and solvents provide most of the cleaning benefits, and the surfactants may leave some residual hydrophilization benefit to the surface.
  • Hydrophilization can improve the ease of cleaning, by tending to repel any hydrophobic soils from adhering strongly to a surface.
  • the ease of cleaning benefit if present is short lived, since upon any rinsing or wiping the surfactant may be easily rinsed away. This is particularly true in the case of hydrophobic surfaces. Hydrophilic surfaces inherently repel hydrophobic soils to some degree. Less polar or non-polar surfaces, however, do not naturally possess attributes for repelling soils which are typically hydrophobic in nature.
  • the present invention is directed to an aqueous hard surface cleaner composition
  • an aqueous hard surface cleaner composition comprising:
  • a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof,
  • a germicidal agent which may be absent if the surfactant comprises a quaternary ammonium surfactant
  • hydrophilic polymer comprising styrene sulfonate repeating units
  • composition exhibits a pH of greater than or equal to about 6.
  • the present invention is directed to a method for cleaning a hard surface, comprising contacting the hard surface with the above described aqueous hard surface cleaner.
  • composition of the present invention provides an easier cleaning benefit, wherein easier cleaning is identified by comparing the ease of removing a soil from a surface which had, prior to soiling, been cleaned with the hard surface cleaner composition of the present invention to the ease of removing a soil from the surface which had, prior to soiling, been cleaned with the hard surface cleaner that lacks the hydrophilic polymer component of, but is otherwise analogous to the hard surface cleaner composition of the present invention.
  • Suitable hard surfaces are smooth, substantially non porous surfaces including, for example, glass, ceramic, organic polymer, metal, or wood.
  • the hard surface cleaner composition of the present invention comprises, based on 100 parts by weight (pbw) of such composition,
  • Nonionic surfactants are surfactant compounds that do not dissociate into ions and that do not have an electrical charge associated with them.
  • Suitable nonionic surfactants are generally known in the art and include, for example, compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
  • nonionic surfactants include the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols, fatty acid amide surfactants, polyhydroxy fatty acid amide surfactants, amine oxide surfactants, alkyl ethoxylate surfactants, alkanoyl glucose amide surfactants, alkanolamides surfactants, alkylpolyglycosides, and condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide.
  • nonionic surfactants include alkanolamides such as cocamide DEA, cocamide MEA, cocamide MIPA, PEG-5 cocamide MEA, lauramide DEA, and lauramide MEA; alkyl amine oxides such as lauramine oxide, cocamine oxide, cocamidopropylamine oxide, and lauramidopropylamine oxide; polysorbates and ethoxylated sorbitan esters such as sorbitan laurate, sorbitan distearate, PEG-80 sorbitan laurate, polysorbate-20, and polysorbate-80; fatty acids or fatty acid esters such as lauric acid, isostearic acid, and PEG-150 distearate; fatty alcohols or ethoxylated fatty alcohols such as lauryl alcohol, laureth-4, laureth-7, laureth-9, laureth-40, trideceth alcohol, C11-15 pareth-9, C12-13 Pareth-3, and
  • Cationic surfactants are ionic surfactant compounds that have a positive electrical charge associated with the hydrophilic portion of the surfactant.
  • Suitable cationic surfactants are generally known in the art and include, for example, compounds according to formula (1) below:
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen, an organic group, provided that at least one of R 1 , R 2 , R 3 and R 4 is not hydrogen.
  • X ⁇ is an anion
  • Suitable anions include, for example, chloride, bromide, methosulfate, ethosulfate, lactate, saccharinate, acetate or phosphate.
  • R 1 , R 2 , R 3 and R 4 groups are hydrogen
  • the compound may be referred to as an amine salt.
  • cationic amine salts include polyethoxylated (2) oleyl/stearyl amine, ethoxylated tallow amine, cocoalkylamine, oleylamine, and tallow alkyl amine as well as mixtures thereof.
  • R 1 , R 2 , R 3 , and R 4 may each independently be the same or different organic group, or alternatively, may be fused with another one of the R 1 , R 2 , R 3 and R 4 groups to form, together with the nitrogen atom to which they are attached, a heterocyclic ring, but may not be hydrogen.
  • Suitable organic groups include, for example, alkyl, alkoxy, hydroxyalkyl, and aryl, each of which may be further substituted with other organic groups.
  • Suitable quaternary ammonium compounds include monoalkyl amine derivatives, dialkyl amine derivatives, and imidazoline derivatives, as well as mixtures thereof.
  • Suitable monoalkyl amine derivatives include, for example, cetyl trimethyl ammonium bromide (also known as cetrimonium bromide or CETAB), cetyl trimethyl ammonium chloride (also known as cetrimonium chloride), myristyl trimethyl ammonium bromide (also known as myrtrimonium bromide or Quaternium-13), stearyl dimethyl benzyl ammonium chloride (also known as stearalkonium chloride), oleyl dimethyl benzyl ammonium chloride, (also known as olealkonium chloride), lauryl/myristryl trimethyl ammonium methosulfate (also known as cocotrimonium methosulfate), cetyl-dimethyl-(2)hydroxyethyl ammonium dihydrogen phosphate (also known as hydroxyethyl cetyldimonium phosphate), bassuamidopropylkonium chloride, cocotrimonium chloride, di
  • Suitable dialkyl amine derivatives include, for example, distearyidimonium chloride, dicetyl dimonium chloride, stearyl octyldimonium methosulfate, dihydrogenated palmoylethyl hydroxyethylmonium methosulfate, dipalmitoylethyl hydroxyethylmonium methosulfate, dioleoylethyl hydroxyethylmonium methosulfate, hydroxypropyl bisstearyldimonium chloride, and mixtures thereof.
  • Suitable imidazoline derivatives include, for example, isostearyl benzylimidonium chloride, cocoyl benzyl hydroxyethyl imidazolinium chloride, cocoyl hydroxyethylimidazolinium PG-chloride phosphate, Quatemium 32, and stearyl hydroxyethylimidonium chloride, and mixtures thereof.
  • Amphoteric surfactants are ionic surfactant compounds that are characterized by the presence of two ionic sites on the same molecule and which, depending on the pH of the surrounding medium, may carry a negative electrical charge, a positive electrical charge, or both a negative electrical charge and a positive electrical charge on the same molecule.
  • Suitable amphoteric surfactants are generally known in the art and include, for example, derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched, may be saturated or unsaturated, and wherein one of the aliphatic substituents contains from about 8 to about 22 carbon atoms and one contains an anionic water solubilizing group.
  • amphoteric surfactants include the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts of alkyl amphocarboxy glycinates and alkyl amphocarboxypropionates, alkyl amphodipropionates, alkyl amphodiacetates, alkyl amphoglycinates and alkyl amphopropionates, as well as alkyl iminopropionates, alkyl iminodipropionates and alkyl amphopropylsulfonates.
  • Amphoteric surfactants are typically associated with a counterion, such as, for example, a sodium, magnesium, potassium, ammonium, or substituted ammonium cation.
  • amphoteric surfactants include sodium cocoamphoacetate, sodium cocoamphopropionate, disodium cocoamphodiacetate, diammonium cocoaphodiacetate, sodium lauroamphoacetate, disodium lauroamphodiacetate, dipotassium lauroamphodiacetate, dimagnesium lauroamphodiacetate, disodium lauroamphodipropionate, disodium cocoamphopropyl sulfonate caproamphodiacetate, sodium caproamphoacetate, disodium caproamphodipropionate, and sodium stearoamphoacetate, and triethanolamine steroamphoacetate, as well as mixtures thereof.
  • Zwitterionic surfactants are ionic surfactant compounds characterized by the presence of two ionic sites per molecule, wherein one of the ionic sites carries a positive electrical charge regardless of the pH of the surrounding medium and wherein the other ionic site may, depending on the pH of the surrounding medium, carry a positive charge.
  • Suitable zwitterionic surfactants are generally known in the art and include, for example, those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic radicals may be straight chain or branched, may saturated or unsaturated, and wherein one of the aliphatic substituents contains from about 8 to 22 carbon atoms and one contains an anionic water-solubilizing group such as carboxyl, sulfonate, sulfate, phosphate or phosphonate.
  • suitable Zwitterionic surfactants include alkyl betaines, such as cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxy-ethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxy-ethyl)carboxy methyl betaine, stearyl bis-(2-hydroxy-propyl)carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, amidopropyl betaines, and alkyl sultaines, such as cocodimethyl sulfopropyl betaine, stearyldimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxy-ethyl)sulfopropyl betaine,
  • the germicidal component of the hard surface cleaner of the present invention may be any compound which exhibits germicidal activity, that is, is capable of killing bacteria and/or retarding bacterial growth, on a hard surface to which the hard surface cleaner of the resent invention is applied, including, for example, sodium hypochlorite and quaternary ammonium compounds.
  • a germicidally effective amount of a quaternary ammonium compound is typically from about 0.01 to about 10 pbw, more typically from about 0.01 to about 3 pbw quaternary ammonium compound per 100 pbw of the hard surface cleaner composition of the present invention.
  • Quaternary ammonium compounds suitable for use as the germicidal agent of the hard surface cleaner of the present invention include the quaternary ammonium surfactants described above. If the surfactant component of the composition of the present invention comprises at least a germicidally effective amount of a quaternary ammonium surfactant, then such quaternary ammonium surfactant may also function as the germicidal agent, in which case no separate germicidal agent is required.
  • the primary surfactant is selected from semi-polar nonionic surfactants, alkylbetaine or sulfobetaine amphoteric surfactants, and mixtures thereof.
  • the hard surface cleaner composition of the present invention may, optionally, further comprise a water soluble organic solvent.
  • Suitable water soluble organic solvents are generally known in the art and include, for example, (C 1 -C 6 )alkanols, (C 1 -C 6 )diols, (C 3 -C 24 )alkylene glycol ethers, and mixtures thereof.
  • the composition of the present invention further comprises up to about 10 pbw of a water soluble organic solvent per 100 pbw of the hard surface cleaner composition of the present invention.
  • the hard surface cleaner composition of the present invention may, optionally, further comprise a chelating agent.
  • Suitable chelating agents for chelating metal atoms are generally know in the art and include, for example, aminophosphonate chelating agents, and ethylenediamine tetraacetic acid.
  • Suitable aminophosphonate chelating agents include, for example, ethylene diaminetetramethylene phsophonates, diethylene triamine pentamethylene phosphonate
  • the chelating agent comprises ethylenediamine tetraacetic acid.
  • the composition of the present invention further comprises, based on 100 pbw of the hard surface cleaner composition of the present invention, from about 0.01 to about 10 pbw, more typically from about 0.1 to about 3 pbw, of a chelating agent.
  • the hydrophilic polymer of the present invention may be any polymer that contains styrenesulfonate repeating units, including styrenesulfonate homopolymers, such as poly(sodium 4-styrenesulfonate) polymers, as well as copolymers that contain styrenesulfonate repeating units copolymerized with repeating units derived from one or more other monoethylenically unsaturated monomers.
  • styrenesulfonate homopolymers such as poly(sodium 4-styrenesulfonate) polymers, as well as copolymers that contain styrenesulfonate repeating units copolymerized with repeating units derived from one or more other monoethylenically unsaturated monomers.
  • Suitable ethylenically unsaturated monomers include, for example, styrene, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, vinyl acetic acid, maleic acid, fumaric acid, (C 1 -C 4 )alkyl esters of acrylic acid or methacrylic acid, such as methyl acrylate and methyl methacrylate, (C 1 -C 4 )hydroxyalkyl esters of acrylic acid or methacrylic acid, such as hydroxyethyl methacrylate.
  • Suitable copolymers include random copolymers, graft copolymers and block copolymers, such as, for example, poly(styrenesulfonic acid co-maleic acid) sodium salt, poly(sodium 4-styrenesulfonate)-poly(styrene) random copolymers, poly(sodium 4-styrenesulfonate)-b-poly(acrylamide) block copolymers, poly(sodium 4-styrenesulfonate)-b-poly(styrene) block copolymers, poly(sodium 4-styrenesulfonate)-b-poly(hydroxyethylmethacrylate) block copolymers, and poly(sodium 4-styrenesulfonate)-b-poly(methacrylic acid) block copolymers.
  • block copolymers such as, for example, poly(styrenesulfonic acid co-maleic acid) sodium
  • a suitable copolymer comprises, on average,, greater than or equal to about 1 mole styrene sulfonate repeating units per 100 moles of repeating units of the copolymer.
  • the comonomer of such copolymer is a hydrophobic comonomer, such as for example, styrene
  • such copolymers more typically comprise, on average, greater than or equal to about 20 moles, even more typically 40 moles, styrene sulfonate repeating unit per 100 moles of repeating units of the copolymer.
  • the hydrophilic polymer exhibits a weight average molecular weight (MW) of greater than or equal to about 1000, more typically of from about 5,000 to about 5,000,000, and even more typically of from about 10,000 to about 2,000,000, as determined by gel permeation chromatography (GPC).
  • MW weight average molecular weight
  • the hard surface cleaner composition of the present invention exhibits a pH of from about 7 to about 14, more typically a pH of from about 7 to about 13, and even more typically a pH of from about 8 to about 13.
  • the hard surface cleaner composition of the present invention may, optionally, further comprise up to about 10 pbw per 100 pbw of the hard surface cleaner composition of other ingredients, such as for example, fragrances, colorants, opacifiers, bleaching agents, pH modifiers, detergent enzymes, stabilizers, germicidally active components, thickeners, hydrotropes.
  • other ingredients such as for example, fragrances, colorants, opacifiers, bleaching agents, pH modifiers, detergent enzymes, stabilizers, germicidally active components, thickeners, hydrotropes.
  • the hard surface cleaner composition of the present invention is made by combining and mixing desired appropriate relative amounts of the above described components.
  • a hard surface is contacted with the hard surface cleaner of the present invention and the hard surface cleaner composition and the surface is rinsed with water or wiped and allowed to dry.
  • a scrub tester apparatus was used.
  • the scrub tester consisted of a wooden panel (about 40 cm in length) with rails to hold 8 samples tile in a single row, and a metal track with rails for guiding a sponge holder placed over the panel in order to wipe tiles.
  • Formula 409 Antibacterial Formulation
  • All Purpose Cleaner was used as comparative Example C1 and Fantastik All Purpose Cleaner was used as comparative Examples C2.
  • the Formula 409 cleaner exhibited a pH of about 12.3.
  • the Fantastik cleaner exhibited a pH of about 12.2.
  • the cleaner compositions of Examples 1-10 each included 1 wt % hydrophilic polymer and were made by adding the hydrophilic polymer listed in TABLE I below to Formula 409 (Antibacterial Formulation) All Purpose Cleaner (Clorox). The pH of each of the compositions of Examples 1-10 was adjusted to a value of 12.3 ⁇ 0.1.
  • Substrate tiles (5 cm ⁇ 5 cm white FormicaTM laminate squares mounted on 1.3 cm thick particle board) were pre-cleaned by the addition of 0.1 mL of ethanol onto the surface of the tile and wiped with paper towel. The tiles are allowed to dry at room temperature for at least 30 min.
  • the substrate tiles were treated as follows. 1.0 mL of a treatment formulations listed in the TABLE below was pipetted onto the surface of a pre-cleaned tile. The formulation was spread over the entire upper surface of the tile and allowed to remain on the surface of the tile for five minutes. The upper surfaces of the tiles were then wiped three times with each side of a water dampened 4 cm ⁇ 4 cm cellulosic sponge and allowed to dry at room temperature for 2-3 hours.
  • a test soil was made by combining 20.0 g of a curing agent and 90 g of a soil stock and mixing the combination for 4-5 hours.
  • the soil stock was made by mixing 60 g sunflower oil, 10 g olive oil, and 20 g iron oxide pigment in a 150 ml plastic beaker with stir bar at room temperature for approximately 30 min.
  • a curing agent was made by mixing 45 g isooctane and 1 g cobalt naphthenate in a 150 ml plastic beaker with stir bar at room temperature for approximately 30 min.
  • Lightly soiled substrate tiles were prepared as follows. Eight tiles were mounted in the scrub tester. A 4 inch wide soft rubber ink roller was dampened with the test soil. Single drops of test soil were applied to the third and fifth tiles and the drops were then spread evenly over the four inner tiles using the dampened roller. The tiles were placed in a constant temperature and humidity chamber (25° C., 50% RH) for 24 h.
  • Heavily soiled substrate tiles were prepared as follows. Eight tiles were mounted in the scrub tester. Single drops of test soil were deposited on the third and fifth tiles and the drops were spread over the four inner tiles using a soil dampened 4 inch wide soft rubber ink roller. Single drops of test soil were then deposited on the second and fourth tiles and the drops were spread over the four inner tiles using the soil dampened roller. The tiles were then placed in a constant temperature and humidity chamber (25° C., 50% RH) for 24 h.
  • the soiled substrate tiles were scrubbed. Eight tiles were mounted in the scrub tested. In each case, the four inner tiles were the test specimens of interest and the outer tile were simply place holders. A 4 cm ⁇ 9 cm cellulosic sponge was rinsed in water and rung out by hand, so that it was damp but is not dripping wet. The sponge was placed into the metal sponge holder. The cleaner was sprayed a few times so there is a consistent strong spray for the test. The first two soiled tiles were sprayed once (about 1.3 g) with cleaner from about 4 inches away. Immediately spray the second two soiled tiles were then sprayed once with cleaner from about four inches away.
  • a hard surface cleaner composition is made by combining the ingredients listed below in TABLE II in the relative amounts set forth in TABLE II.
  • TABLE II Amount (pbw per 100 pbw Ingredient composition) Na 4 EDTA 0.5 Tallow Benzyl Quat (Lonza) 0.27 Rhodasurf LA-7 2.25 poly(sodium 4-styrenesulfonate) 1 MW 1,000,000 Water Balance to 100 pbw

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Abstract

An aqueous hard surface cleaner composition contains a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof, a germicidal agent, which may be absent if the surfactant comprises a quaternary ammonium surfactant, a hydrophilic polymer comprising styrene sulfonate repeating units, and water, wherein the composition exhibits a pH of greater than or equal to about 6, and provides an easier cleaning benefit.

Description

    FIELD OF THE INVENTION
  • This invention relates to the use of sulfonated polystyrene polymers in hard surface cleaners. [0001]
    • BACKGROUND OF THE INVENTION
  • Hard surface cleaners typically contain nonionic surfactants, an anti-bacterial agent (which may be a quaternary ammonium type surfactant), chelating agents, a solvent, and water. Optionally, anionic surfactants may be used in which case the anti-bacterial agent may be excluded or replaced by something other than a quaternary ammonium-type surfactant. The most common surfactant systems for household cleaners are alkyl polyglucosides, or alkyl ethoxylates. [0002]
  • Hard surface cleaners are formulated so as to provide cleaning benefit, with little or no foam, and very fast drying so as to leave little or no streaking or residue. The surfactants and solvents provide most of the cleaning benefits, and the surfactants may leave some residual hydrophilization benefit to the surface. Hydrophilization can improve the ease of cleaning, by tending to repel any hydrophobic soils from adhering strongly to a surface. However, the ease of cleaning benefit if present is short lived, since upon any rinsing or wiping the surfactant may be easily rinsed away. This is particularly true in the case of hydrophobic surfaces. Hydrophilic surfaces inherently repel hydrophobic soils to some degree. Less polar or non-polar surfaces, however, do not naturally possess attributes for repelling soils which are typically hydrophobic in nature. [0003]
    • SUMMARY OF THE INVENTION
  • In one aspect, the present invention is directed to an aqueous hard surface cleaner composition comprising: [0004]
  • a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof, [0005]
  • a germicidal agent, which may be absent if the surfactant comprises a quaternary ammonium surfactant, [0006]
  • a hydrophilic polymer comprising styrene sulfonate repeating units, and [0007]
  • water, [0008]
  • wherein the composition exhibits a pH of greater than or equal to about 6. [0009]
  • In another aspect, the present invention is directed to a method for cleaning a hard surface, comprising contacting the hard surface with the above described aqueous hard surface cleaner. [0010]
  • The composition of the present invention provides an easier cleaning benefit, wherein easier cleaning is identified by comparing the ease of removing a soil from a surface which had, prior to soiling, been cleaned with the hard surface cleaner composition of the present invention to the ease of removing a soil from the surface which had, prior to soiling, been cleaned with the hard surface cleaner that lacks the hydrophilic polymer component of, but is otherwise analogous to the hard surface cleaner composition of the present invention.[0011]
    • DETAILED DESCRIPTION OF INVENTION AND PREFERRED EMBODIMENTS
  • Suitable hard surfaces are smooth, substantially non porous surfaces including, for example, glass, ceramic, organic polymer, metal, or wood. [0012]
  • In one embodiment, the hard surface cleaner composition of the present invention comprises, based on 100 parts by weight (pbw) of such composition, [0013]
  • from about 0.01 to about 10 pbw, more typically from about 0.01 to about 5 pbw, of the surfactant, [0014]
  • a germicdally effective amount of the germicidal agent, [0015]
  • from about 0.01 to about 10 pbw, more typically from about 0.01 to about 3 pbw, of the hydrophilic polymer, and [0016]
  • and water [0017]
  • Nonionic surfactants are surfactant compounds that do not dissociate into ions and that do not have an electrical charge associated with them. Suitable nonionic surfactants are generally known in the art and include, for example, compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature. Examples of useful nonionic surfactants include the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols, fatty acid amide surfactants, polyhydroxy fatty acid amide surfactants, amine oxide surfactants, alkyl ethoxylate surfactants, alkanoyl glucose amide surfactants, alkanolamides surfactants, alkylpolyglycosides, and condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. Specific examples of suitable nonionic surfactants include alkanolamides such as cocamide DEA, cocamide MEA, cocamide MIPA, PEG-5 cocamide MEA, lauramide DEA, and lauramide MEA; alkyl amine oxides such as lauramine oxide, cocamine oxide, cocamidopropylamine oxide, and lauramidopropylamine oxide; polysorbates and ethoxylated sorbitan esters such as sorbitan laurate, sorbitan distearate, PEG-80 sorbitan laurate, polysorbate-20, and polysorbate-80; fatty acids or fatty acid esters such as lauric acid, isostearic acid, and PEG-150 distearate; fatty alcohols or ethoxylated fatty alcohols such as lauryl alcohol, laureth-4, laureth-7, laureth-9, laureth-40, trideceth alcohol, C11-15 pareth-9, C12-13 Pareth-3, and C14-15 Pareth-11, as well as mixtures thereof. [0018]
  • Cationic surfactants are ionic surfactant compounds that have a positive electrical charge associated with the hydrophilic portion of the surfactant. Suitable cationic surfactants are generally known in the art and include, for example, compounds according to formula (1) below: [0019]
    Figure US20040194800A1-20041007-C00001
  • wherein: [0020]
  • R[0021] 1, R2, R3 and R4, are each independently hydrogen, an organic group, provided that at least one of R1, R2, R3 and R4 is not hydrogen.
  • X[0022] − is an anion.
  • Suitable anions include, for example, chloride, bromide, methosulfate, ethosulfate, lactate, saccharinate, acetate or phosphate. [0023]
  • If one to three of the R[0024] 1, R2, R3 and R4 groups are hydrogen, then the compound may be referred to as an amine salt. Some examples of cationic amine salts include polyethoxylated (2) oleyl/stearyl amine, ethoxylated tallow amine, cocoalkylamine, oleylamine, and tallow alkyl amine as well as mixtures thereof.
  • For quaternary ammonium compounds (generally referred to as “quats”) R[0025] 1, R2, R3, and R4 may each independently be the same or different organic group, or alternatively, may be fused with another one of the R1, R2, R3 and R4 groups to form, together with the nitrogen atom to which they are attached, a heterocyclic ring, but may not be hydrogen. Suitable organic groups include, for example, alkyl, alkoxy, hydroxyalkyl, and aryl, each of which may be further substituted with other organic groups. Suitable quaternary ammonium compounds include monoalkyl amine derivatives, dialkyl amine derivatives, and imidazoline derivatives, as well as mixtures thereof.
  • Suitable monoalkyl amine derivatives include, for example, cetyl trimethyl ammonium bromide (also known as cetrimonium bromide or CETAB), cetyl trimethyl ammonium chloride (also known as cetrimonium chloride), myristyl trimethyl ammonium bromide (also known as myrtrimonium bromide or Quaternium-13), stearyl dimethyl benzyl ammonium chloride (also known as stearalkonium chloride), oleyl dimethyl benzyl ammonium chloride, (also known as olealkonium chloride), lauryl/myristryl trimethyl ammonium methosulfate (also known as cocotrimonium methosulfate), cetyl-dimethyl-(2)hydroxyethyl ammonium dihydrogen phosphate (also known as hydroxyethyl cetyldimonium phosphate), bassuamidopropylkonium chloride, cocotrimonium chloride, distearyldimonium chloride, wheat germ-amidopropalkonium chloride, stearyl octyldimonium methosulfate, isostearaminopropal-konium chloride, dihydroxypropyl PEG-5 linoleaminium chloride, PEG-2 stearmonium chloride, Quaternium 18, Quaternium 80, Quaternium 82, Quaternium 84, behentrimonium chloride, dicetyl dimonium chloride, behentrimonium methosulfate, tallow trimonium chloride, and behenamidopropyl ethyl dimonium ethosulfate, as well as mixtures thereof. [0026]
  • Suitable dialkyl amine derivatives include, for example, distearyidimonium chloride, dicetyl dimonium chloride, stearyl octyldimonium methosulfate, dihydrogenated palmoylethyl hydroxyethylmonium methosulfate, dipalmitoylethyl hydroxyethylmonium methosulfate, dioleoylethyl hydroxyethylmonium methosulfate, hydroxypropyl bisstearyldimonium chloride, and mixtures thereof. [0027]
  • Suitable imidazoline derivatives include, for example, isostearyl benzylimidonium chloride, cocoyl benzyl hydroxyethyl imidazolinium chloride, cocoyl hydroxyethylimidazolinium PG-chloride phosphate, Quatemium 32, and stearyl hydroxyethylimidonium chloride, and mixtures thereof. [0028]
  • Amphoteric surfactants are ionic surfactant compounds that are characterized by the presence of two ionic sites on the same molecule and which, depending on the pH of the surrounding medium, may carry a negative electrical charge, a positive electrical charge, or both a negative electrical charge and a positive electrical charge on the same molecule. Suitable amphoteric surfactants are generally known in the art and include, for example, derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical may be straight chain or branched, may be saturated or unsaturated, and wherein one of the aliphatic substituents contains from about 8 to about 22 carbon atoms and one contains an anionic water solubilizing group. Specific examples of suitable amphoteric surfactants include the alkali metal, alkaline earth metal, ammonium or substituted ammonium salts of alkyl amphocarboxy glycinates and alkyl amphocarboxypropionates, alkyl amphodipropionates, alkyl amphodiacetates, alkyl amphoglycinates and alkyl amphopropionates, as well as alkyl iminopropionates, alkyl iminodipropionates and alkyl amphopropylsulfonates. Amphoteric surfactants are typically associated with a counterion, such as, for example, a sodium, magnesium, potassium, ammonium, or substituted ammonium cation. Specific examples of some suitable amphoteric surfactants include sodium cocoamphoacetate, sodium cocoamphopropionate, disodium cocoamphodiacetate, diammonium cocoaphodiacetate, sodium lauroamphoacetate, disodium lauroamphodiacetate, dipotassium lauroamphodiacetate, dimagnesium lauroamphodiacetate, disodium lauroamphodipropionate, disodium cocoamphopropyl sulfonate caproamphodiacetate, sodium caproamphoacetate, disodium caproamphodipropionate, and sodium stearoamphoacetate, and triethanolamine steroamphoacetate, as well as mixtures thereof. [0029]
  • Zwitterionic surfactants are ionic surfactant compounds characterized by the presence of two ionic sites per molecule, wherein one of the ionic sites carries a positive electrical charge regardless of the pH of the surrounding medium and wherein the other ionic site may, depending on the pH of the surrounding medium, carry a positive charge. Suitable zwitterionic surfactants are generally known in the art and include, for example, those which can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic radicals may be straight chain or branched, may saturated or unsaturated, and wherein one of the aliphatic substituents contains from about 8 to 22 carbon atoms and one contains an anionic water-solubilizing group such as carboxyl, sulfonate, sulfate, phosphate or phosphonate. Specific examples of suitable Zwitterionic surfactants include alkyl betaines, such as cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxy-ethyl betaine, cetyl dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxy-ethyl)carboxy methyl betaine, stearyl bis-(2-hydroxy-propyl)carboxymethyl betaine, oleyl dimethyl gamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, amidopropyl betaines, and alkyl sultaines, such as cocodimethyl sulfopropyl betaine, stearyldimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxy-ethyl)sulfopropyl betaine, and alkylamidopropylhydroxy sultaines, as well as mixtures thereof. [0030]
  • The germicidal component of the hard surface cleaner of the present invention may be any compound which exhibits germicidal activity, that is, is capable of killing bacteria and/or retarding bacterial growth, on a hard surface to which the hard surface cleaner of the resent invention is applied, including, for example, sodium hypochlorite and quaternary ammonium compounds. [0031]
  • A germicidally effective amount of a quaternary ammonium compound is typically from about 0.01 to about 10 pbw, more typically from about 0.01 to about 3 pbw quaternary ammonium compound per 100 pbw of the hard surface cleaner composition of the present invention. [0032]
  • Quaternary ammonium compounds suitable for use as the germicidal agent of the hard surface cleaner of the present invention include the quaternary ammonium surfactants described above. If the surfactant component of the composition of the present invention comprises at least a germicidally effective amount of a quaternary ammonium surfactant, then such quaternary ammonium surfactant may also function as the germicidal agent, in which case no separate germicidal agent is required. [0033]
  • In one embodiment, the primary surfactant is selected from semi-polar nonionic surfactants, alkylbetaine or sulfobetaine amphoteric surfactants, and mixtures thereof. [0034]
  • The hard surface cleaner composition of the present invention may, optionally, further comprise a water soluble organic solvent. Suitable water soluble organic solvents are generally known in the art and include, for example, (C[0035] 1-C6)alkanols, (C1-C6)diols, (C3-C24)alkylene glycol ethers, and mixtures thereof. In one embodiment, the composition of the present invention further comprises up to about 10 pbw of a water soluble organic solvent per 100 pbw of the hard surface cleaner composition of the present invention.
  • The hard surface cleaner composition of the present invention may, optionally, further comprise a chelating agent. Suitable chelating agents for chelating metal atoms are generally know in the art and include, for example, aminophosphonate chelating agents, and ethylenediamine tetraacetic acid. Suitable aminophosphonate chelating agents include, for example, ethylene diaminetetramethylene phsophonates, diethylene triamine pentamethylene phosphonate In one embodiment, the chelating agent comprises ethylenediamine tetraacetic acid. In one embodiment, the composition of the present invention further comprises, based on 100 pbw of the hard surface cleaner composition of the present invention, from about 0.01 to about 10 pbw, more typically from about 0.1 to about 3 pbw, of a chelating agent. [0036]
  • The hydrophilic polymer of the present invention may be any polymer that contains styrenesulfonate repeating units, including styrenesulfonate homopolymers, such as poly(sodium 4-styrenesulfonate) polymers, as well as copolymers that contain styrenesulfonate repeating units copolymerized with repeating units derived from one or more other monoethylenically unsaturated monomers. Suitable ethylenically unsaturated monomers include, for example, styrene, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, vinyl acetic acid, maleic acid, fumaric acid, (C[0037] 1-C4)alkyl esters of acrylic acid or methacrylic acid, such as methyl acrylate and methyl methacrylate, (C1-C4)hydroxyalkyl esters of acrylic acid or methacrylic acid, such as hydroxyethyl methacrylate. Suitable copolymers include random copolymers, graft copolymers and block copolymers, such as, for example, poly(styrenesulfonic acid co-maleic acid) sodium salt, poly(sodium 4-styrenesulfonate)-poly(styrene) random copolymers, poly(sodium 4-styrenesulfonate)-b-poly(acrylamide) block copolymers, poly(sodium 4-styrenesulfonate)-b-poly(styrene) block copolymers, poly(sodium 4-styrenesulfonate)-b-poly(hydroxyethylmethacrylate) block copolymers, and poly(sodium 4-styrenesulfonate)-b-poly(methacrylic acid) block copolymers.
  • In one embodiment, a suitable copolymer comprises, on average,, greater than or equal to about 1 mole styrene sulfonate repeating units per 100 moles of repeating units of the copolymer. In those embodiments wherein the comonomer of such copolymer is a hydrophobic comonomer, such as for example, styrene, such copolymers more typically comprise, on average, greater than or equal to about 20 moles, even more typically 40 moles, styrene sulfonate repeating unit per 100 moles of repeating units of the copolymer. [0038]
  • In one embodiment, the hydrophilic polymer exhibits a weight average molecular weight (MW) of greater than or equal to about 1000, more typically of from about 5,000 to about 5,000,000, and even more typically of from about 10,000 to about 2,000,000, as determined by gel permeation chromatography (GPC). [0039]
  • In one embodiment, the hard surface cleaner composition of the present invention exhibits a pH of from about 7 to about 14, more typically a pH of from about 7 to about 13, and even more typically a pH of from about 8 to about 13. [0040]
  • The hard surface cleaner composition of the present invention may, optionally, further comprise up to about 10 pbw per 100 pbw of the hard surface cleaner composition of other ingredients, such as for example, fragrances, colorants, opacifiers, bleaching agents, pH modifiers, detergent enzymes, stabilizers, germicidally active components, thickeners, hydrotropes. [0041]
  • The hard surface cleaner composition of the present invention is made by combining and mixing desired appropriate relative amounts of the above described components. [0042]
  • In one embodiment of the method of the present invention, a hard surface is contacted with the hard surface cleaner of the present invention and the hard surface cleaner composition and the surface is rinsed with water or wiped and allowed to dry. [0043]
  • Use of the hard surface cleaner to clean a hard surface renders the surface easier to clean in subsequent cleaning activities. While not wishing to be bound by theory, it is believed that some of the hydrophilic polymer component of the cleaner composition remains on the surface after cleaning and disrupts interaction between the surface and hydrophobic soil that subsequently comes into contact with the surface, thus rendering the soil easier to remove from the surface. [0044]
    • EXAMPLES 1-10 AND COMPARATIVE EXAMPLES C1 AND C2
  • The easier cleaning benefit provided by treatment of a hard surface with a polymer comprising styrenesulfonate repeating units was measured by treating the surface of Formica laminate tiles with such polymers, soiling the surfaces, and then scrubbing the surfaces and rating the level of cleanliness of the scrubbed surfaces. [0045]
  • A scrub tester apparatus was used. The scrub tester consisted of a wooden panel ( about 40 cm in length) with rails to hold 8 samples tile in a single row, and a metal track with rails for guiding a sponge holder placed over the panel in order to wipe tiles. [0046]
  • Formula 409 (Antibacterial Formulation) All Purpose Cleaner was used as comparative Example C1 and Fantastik All Purpose Cleaner was used as comparative Examples C2. The Formula 409 cleaner exhibited a pH of about 12.3. The Fantastik cleaner exhibited a pH of about 12.2. [0047]
  • The cleaner compositions of Examples 1-10 each included 1 wt % hydrophilic polymer and were made by adding the hydrophilic polymer listed in TABLE I below to Formula 409 (Antibacterial Formulation) All Purpose Cleaner (Clorox). The pH of each of the compositions of Examples 1-10 was adjusted to a value of 12.3±0.1. [0048]
  • Substrate tiles (5 cm×5 cm white Formica™ laminate squares mounted on 1.3 cm thick particle board) were pre-cleaned by the addition of 0.1 mL of ethanol onto the surface of the tile and wiped with paper towel. The tiles are allowed to dry at room temperature for at least 30 min. [0049]
  • The substrate tiles were treated as follows. 1.0 mL of a treatment formulations listed in the TABLE below was pipetted onto the surface of a pre-cleaned tile. The formulation was spread over the entire upper surface of the tile and allowed to remain on the surface of the tile for five minutes. The upper surfaces of the tiles were then wiped three times with each side of a water dampened 4 cm×4 cm cellulosic sponge and allowed to dry at room temperature for 2-3 hours. [0050]
  • A test soil was made by combining 20.0 g of a curing agent and 90 g of a soil stock and mixing the combination for 4-5 hours. The soil stock was made by mixing 60 g sunflower oil, 10 g olive oil, and 20 g iron oxide pigment in a 150 ml plastic beaker with stir bar at room temperature for approximately 30 min. A curing agent was made by mixing 45 g isooctane and 1 g cobalt naphthenate in a 150 ml plastic beaker with stir bar at room temperature for approximately 30 min. [0051]
  • Lightly soiled substrate tiles were prepared as follows. Eight tiles were mounted in the scrub tester. A 4 inch wide soft rubber ink roller was dampened with the test soil. Single drops of test soil were applied to the third and fifth tiles and the drops were then spread evenly over the four inner tiles using the dampened roller. The tiles were placed in a constant temperature and humidity chamber (25° C., 50% RH) for 24 h. [0052]
  • Heavily soiled substrate tiles were prepared as follows. Eight tiles were mounted in the scrub tester. Single drops of test soil were deposited on the third and fifth tiles and the drops were spread over the four inner tiles using a soil dampened 4 inch wide soft rubber ink roller. Single drops of test soil were then deposited on the second and fourth tiles and the drops were spread over the four inner tiles using the soil dampened roller. The tiles were then placed in a constant temperature and humidity chamber (25° C., 50% RH) for 24 h. [0053]
  • The soiled substrate tiles were scrubbed. Eight tiles were mounted in the scrub tested. In each case, the four inner tiles were the test specimens of interest and the outer tile were simply place holders. A 4 cm×9 cm cellulosic sponge was rinsed in water and rung out by hand, so that it was damp but is not dripping wet. The sponge was placed into the metal sponge holder. The cleaner was sprayed a few times so there is a consistent strong spray for the test. The first two soiled tiles were sprayed once (about 1.3 g) with cleaner from about 4 inches away. Immediately spray the second two soiled tiles were then sprayed once with cleaner from about four inches away. The sponge in its metal holder was placed on the track and moved from one end of the track to the other for 10 counts (wherein one count is from one end of the track to the other) to scrub the tiles in the scrub tester. The inner tiles were removed from the scrub tester, examined and rated on a scale of 0 to 5 (0-is no removal and 5 is total removal) for soil removal. Results are given in TABLE I below. Each rating is based on the average for 8 cleaned tiles. [0054]
    TABLE I
    Molar ratio
    (Styrene
    sulfonate
    units:comonomer
    Ex. # Styrene Sulfonate Polymer units) Light soil Heavy soil
    C1 None — 1 0.5
    C2 None — 1 0.5
    1 Poly(sodium 4-styrenesulfonate), — 4.3 2.8
    MW = 1,000,000
    2 Poly(sodium 4-styrenesulfonate), — 2 0.5
    MW = 200,000
    3 Poly(sodium 4-styrenesulfonate), — 3.25 1
    MW = 70,000
    4 Poly(styrenesulfonic acid co-maleic acid) 1:1 4 2.8
    sodium salt
    MW = 20,000
    5 Poly(styrenesulfonic acid co-maleic acid) 3:1 4.5 3.8
    sodium salt
    MW = 20,000
    6 Poly(sodium 4-styrenesulfonate)-b-  5.3:94.6 4 0.5
    poly(acrylamide) block copolymer
    5,000 ≦ MW ≦ 30,000
    7 Poly(sodium 4-styrenesulfonate)-b- 92.2:9.6  2.3 3
    poly(styrene) block copolymer
    500 ≦ MW 1,000
    8 Poly(sodium 4-styrenesulfonate)-b- 75:25 2.5 1
    poly(hydroxyethylmethacrylate)
    block copolymer
    5,000 ≦ MW ≦ 10,000
    9 Poly(sodium 4-styrenesulfonate)- 80:20 3.5 1
    poly(methacrylic acid) random copolymer
    MW < 10,000
    10  Poly(sodium 4-styrenesulfonate)-b- 40:60 4.5 3.5
    poly(styrene) random copolymer
    MW = 30,000
    • EXAMPLE 11
  • A hard surface cleaner composition is made by combining the ingredients listed below in TABLE II in the relative amounts set forth in TABLE II. [0055]
    TABLE II
    Amount
    (pbw per 100 pbw
    Ingredient composition)
    Na4EDTA 0.5
    Tallow Benzyl Quat (Lonza) 0.27
    Rhodasurf LA-7 2.25
    poly(sodium 4-styrenesulfonate) 1
    MW = 1,000,000
    Water Balance to 100 pbw

Claims (10)

What is claimed is:
1. An aqueous hard surface cleaner composition, comprising:
a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof,
a germicidal agent, which may be absent if the surfactant comprises a quaternary ammonium surfactant,
a hydrophilic polymer comprising styrene sulfonate repeating units, and
water,
wherein the composition exhibits a pH of greater than or equal to about 6.
2. The composition of claim 1, wherein the composition comprises, based on 100 parts by weight of the composition, from about 0.01 to about 10 parts by weight of the primary surfactant, from about 0.01 to about 10 parts by weight of the germicidal agent, and from about 0.01 to about 1 parts by weight of the hydrophilic polymer.
3. The composition of claim 1, wherein the primary surfactant comprises a nonionic surfactant.
4. The composition of claim 1, wherein the germicidal agent comprises one or more quaternary ammonium surfactants
5. The composition of claim 1, wherein the hydrophilic polymer is a homopolymer of para-styrenesulfonate.
6. The composition of claim 1, wherein the hydrophilic polymer is a copolymer of para-styrenesulfonate and a monomer selected from the group consisting of maleic acid, or salt or anhydride thereof, acrylamide, styrene, polyethylene glycol, hydroxyethyl methacrylate and methacrylic acid, or salt thereof.
7. The composition of claim 1, wherein the hydrophilic polymer comprises at least one polymer selected from poly(sodium 4-styrenesulfonate), poly(styrenesulfonic acid co-maleic acid) sodium salt, poly(sodium 4-styrenesulfonate)-poly(styrene) random copolymer, poly(sodium 4-styrenesulfonate)-b-poly(acrylamide) block copolymer, poly(sodium 4-styrenesulfonate)-b-poly(styrene) block copolymer, poly(sodium 4-styrenesulfonate)-b-poly(hydroxyethylmethacrylate) block copolymer, and poly(sodium 4-styrenesulfonate)-b-poly(methacrylic acid) block copolymer.
8. The composition of claim 1, further comprising a water soluble organic solvent.
9. The composition of claim 1, further comprising a chelating agent.
10. A method for cleaning a hard surface, comprising contacting the hard surface with the aqueous hard surface cleaner of claim 1.
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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060009369A1 (en) * 2000-12-14 2006-01-12 The Clorox Company Cleaning composition
US20060276371A1 (en) * 2005-06-01 2006-12-07 Anthony Schreiner Coacervate systems having soil anti-adhesion and anti-deposition properties on hydrophilic surfaces
US20070179079A1 (en) * 2000-12-14 2007-08-02 Andrew Kilkenny Cleaning Composition
US20080033106A1 (en) * 2006-08-03 2008-02-07 Balint Koroskenyi Composition for improving wettability of surfaces
US20080167411A1 (en) * 2005-02-04 2008-07-10 Agfa Graphics Nv Stable Pigment Dispersions
US20080188612A1 (en) * 2005-02-04 2008-08-07 Agfa Graphics Nv Stable Pigment Dispersions
US20090048143A1 (en) * 2007-08-14 2009-02-19 S. C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
US20110236450A1 (en) * 2010-03-29 2011-09-29 The Clorox Company Polyelectrolyte complexes
US20110236582A1 (en) * 2010-03-29 2011-09-29 Scheuing David R Polyelectrolyte Complexes
US20120056126A1 (en) * 2009-05-21 2012-03-08 Stella Chemifa Corporation Fine-processing agent and fine-processing method
US8975220B1 (en) 2014-08-11 2015-03-10 The Clorox Company Hypohalite compositions comprising a cationic polymer
US8993505B2 (en) 2010-03-29 2015-03-31 The Clorox Company Precursor polyelectrolyte complexes compositions
EP2896637A1 (en) * 2014-01-21 2015-07-22 Rhodia Operations Copolymer comprising units of type A deriving from carboxylic acid monomers and units of type B deriving from sulfonic acid monomers
US9518245B2 (en) 2013-12-16 2016-12-13 3M Innovative Properties Company Detergent and rinse-aid compositions containing a zwitterionic sulfonated silane and methods of using
US9895722B2 (en) 2012-08-31 2018-02-20 3M Innovative Properties Company Method of removing an unwanted constituent from a surface, a method of determining the cleanliness of a hard surface, and a multi-functional composition that includes hydrophilic silane
US20180100123A1 (en) * 2016-10-12 2018-04-12 Mectra Labs, Inc. Cleaning solution
WO2019199886A1 (en) * 2018-04-09 2019-10-17 Rhodia Operations Compositions and methods for long lasting disinfection
WO2020168046A1 (en) * 2019-02-13 2020-08-20 Rhodia Operations Long lasting disinfectant cleaning compositions and methods of use thereof
US11000619B2 (en) 2014-03-28 2021-05-11 S. C. Johnson & Son, Inc. Pump concentrated air freshener
US11130933B2 (en) 2016-01-20 2021-09-28 Rockline Industries, Inc. Wet wipes containing hydroxy acetophenone and cocamidopropyl PG dimonium chloride phosphate

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8795730B2 (en) 2006-01-31 2014-08-05 David John Vachon Compositions and methods for promoting the healing of tissue of multicellular organisms

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4711740A (en) * 1983-04-22 1987-12-08 Lever Brothers Company Detergent compositions
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
US5962388A (en) * 1997-11-26 1999-10-05 The Procter & Gamble Company Acidic aqueous cleaning compositions
US6017561A (en) * 1997-04-04 2000-01-25 The Clorox Company Antimicrobial cleaning composition
US6187731B1 (en) * 1998-12-23 2001-02-13 Henkel Kommandigesellschaft Auf Aktien (Kgaa) Cleaning compositions for hard surfaces containing naphthalene sulfonic acid/formaldehyde condensates
US6225277B1 (en) * 1995-10-09 2001-05-01 The Procter & Gamble Company Hard surface cleaning compositions
US6342473B1 (en) * 1999-01-20 2002-01-29 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkylbenzene sulfonates
US6482392B1 (en) * 1998-07-15 2002-11-19 The Clorox Company Aerosol antimicrobial compositions
US20030109413A1 (en) * 2001-07-11 2003-06-12 Cedric Geffroy Process for cleaning a surface using an aqueous composition containing a dispersed polymer
US6579023B2 (en) * 1998-12-01 2003-06-17 The Procter & Gamble Company Cleaning implements
US20030158078A1 (en) * 2002-02-11 2003-08-21 Jeanne Chang Detergent composition comprising a block copolymer

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU666957B2 (en) * 1992-08-28 1996-02-29 Alcon Laboratories, Inc. Use of certain anionic surfactants to enhance antimicrobial effectiveness of ophthalmic compositions
EP0975728A1 (en) * 1995-10-09 2000-02-02 The Procter & Gamble Company Hard surface cleaning compositions
US5972876A (en) * 1996-10-17 1999-10-26 Robbins; Michael H. Low odor, hard surface cleaner with enhanced soil removal
US6245728B1 (en) * 1996-10-17 2001-06-12 The Clorox Company Low odor, hard surface cleaner with enhanced soil removal
EP0875554B1 (en) * 1997-04-30 2003-06-11 The Procter & Gamble Company Acidic limescale removal compositions
EP1080169A1 (en) * 1998-05-22 2001-03-07 The Procter & Gamble Company Acidic cleaning compositions with c10 alkyl sulfate detergent surfactant
US6200937B1 (en) * 1998-06-09 2001-03-13 Neutrogena Corporation Anti-residue shampoo and liquid toiletry production method
US6107261A (en) * 1999-06-23 2000-08-22 The Dial Corporation Compositions containing a high percent saturation concentration of antibacterial agent
FR2797381B1 (en) * 1999-08-09 2001-11-02 Rhodia Chimie Sa USE OF A WATER-SOLUBLE POLYMER IN A BIOCIDAL COMPOSITION FOR THE TREATMENT OF HARD SURFACES
US6180587B1 (en) * 1999-09-28 2001-01-30 Colgate Palmolive Company Multiple phase compositions

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4711740A (en) * 1983-04-22 1987-12-08 Lever Brothers Company Detergent compositions
US5534198A (en) * 1994-08-02 1996-07-09 The Procter & Gamble Company Glass cleaner compositions having good filming/streaking characteristics and substantive modifier to provide long lasting hydrophilicity
US6225277B1 (en) * 1995-10-09 2001-05-01 The Procter & Gamble Company Hard surface cleaning compositions
US6017561A (en) * 1997-04-04 2000-01-25 The Clorox Company Antimicrobial cleaning composition
US5962388A (en) * 1997-11-26 1999-10-05 The Procter & Gamble Company Acidic aqueous cleaning compositions
US6482392B1 (en) * 1998-07-15 2002-11-19 The Clorox Company Aerosol antimicrobial compositions
US6579023B2 (en) * 1998-12-01 2003-06-17 The Procter & Gamble Company Cleaning implements
US6187731B1 (en) * 1998-12-23 2001-02-13 Henkel Kommandigesellschaft Auf Aktien (Kgaa) Cleaning compositions for hard surfaces containing naphthalene sulfonic acid/formaldehyde condensates
US6342473B1 (en) * 1999-01-20 2002-01-29 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkylbenzene sulfonates
US20030109413A1 (en) * 2001-07-11 2003-06-12 Cedric Geffroy Process for cleaning a surface using an aqueous composition containing a dispersed polymer
US20030158078A1 (en) * 2002-02-11 2003-08-21 Jeanne Chang Detergent composition comprising a block copolymer

Cited By (59)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7741263B2 (en) 2000-12-14 2010-06-22 The Clorox Company Cleaning composition
US20060166849A1 (en) * 2000-12-14 2006-07-27 The Clorox Company Cleaning composition
US20060009369A1 (en) * 2000-12-14 2006-01-12 The Clorox Company Cleaning composition
US7799751B2 (en) 2000-12-14 2010-09-21 The Clorox Company Cleaning composition
US20070179079A1 (en) * 2000-12-14 2007-08-02 Andrew Kilkenny Cleaning Composition
US20070185004A1 (en) * 2000-12-14 2007-08-09 Andrew Kilkenny Cleaning Composition
US7576047B2 (en) 2000-12-14 2009-08-18 The Clorox Company Cleaning composition
US20080167411A1 (en) * 2005-02-04 2008-07-10 Agfa Graphics Nv Stable Pigment Dispersions
US20080188612A1 (en) * 2005-02-04 2008-08-07 Agfa Graphics Nv Stable Pigment Dispersions
US7674843B2 (en) * 2005-02-04 2010-03-09 Agfa Graphics Nv Stable pigment dispersions
US7678845B2 (en) * 2005-02-04 2010-03-16 Agfa Graphics Nv Stable pigment dispersions
EP1888729A2 (en) * 2005-06-01 2008-02-20 Rhodia, Inc. Coacervate systems having soil anti-adhesion and anti-deposition properties on hydrophilic surfaces
WO2006130709A3 (en) * 2005-06-01 2007-05-18 Rhodia Coacervate systems having soil anti-adhesion and anti-deposition properties on hydrophilic surfaces
EP1888729A4 (en) * 2005-06-01 2009-07-08 Rhodia COACERVATION SYSTEMS HAVING ANTI-DEPOSITION PROPERTIES AND ANTI-ADHERENCE OF SOIL ON HYDROPHILIC SURFACES
US20060276371A1 (en) * 2005-06-01 2006-12-07 Anthony Schreiner Coacervate systems having soil anti-adhesion and anti-deposition properties on hydrophilic surfaces
US20080033106A1 (en) * 2006-08-03 2008-02-07 Balint Koroskenyi Composition for improving wettability of surfaces
US7741265B2 (en) 2007-08-14 2010-06-22 S.C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
US20090048143A1 (en) * 2007-08-14 2009-02-19 S. C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
CN102428547A (en) * 2009-05-21 2012-04-25 斯泰拉化工公司 Fine-processing agent and fine-processing method
US8974685B2 (en) * 2009-05-21 2015-03-10 Stella Chemifa Corporation Fine-processing agent and fine-processing method
US20120056126A1 (en) * 2009-05-21 2012-03-08 Stella Chemifa Corporation Fine-processing agent and fine-processing method
US10208275B2 (en) 2010-03-29 2019-02-19 The Clorox Company Polyelectrolyte complexes
US9976109B2 (en) 2010-03-29 2018-05-22 The Clorox Company Precursor polyelectrolyte complexes compositions
US11634667B2 (en) 2010-03-29 2023-04-25 The Clorox Company Precursor polyelectrolyte complex compositions in dual chamber dispensing system
US8993505B2 (en) 2010-03-29 2015-03-31 The Clorox Company Precursor polyelectrolyte complexes compositions
US9012389B2 (en) 2010-03-29 2015-04-21 The Clorox Company Precursor polyelectrolyte complexes compositions
US11578231B2 (en) 2010-03-29 2023-02-14 The Clorox Company Polyelectrolyte complexes
US10968363B2 (en) 2010-03-29 2021-04-06 The Clorox Company Polyelectrolyte complexes
US10858617B2 (en) 2010-03-29 2020-12-08 The Clorox Company Precursor polyelectrolyte complexes compositions
US9273220B2 (en) 2010-03-29 2016-03-01 The Clorox Company Polyelectrolyte complexes
US9309435B2 (en) 2010-03-29 2016-04-12 The Clorox Company Precursor polyelectrolyte complexes compositions comprising oxidants
US9474269B2 (en) 2010-03-29 2016-10-25 The Clorox Company Aqueous compositions comprising associative polyelectrolyte complexes (PEC)
US9486800B2 (en) 2010-03-29 2016-11-08 The Clorox Company Precursor polyelectrolyte complexes compositions
US10563156B2 (en) 2010-03-29 2020-02-18 The Clorox Company Polyelectrolyte complexes
US9593299B2 (en) 2010-03-29 2017-03-14 The Clorox Company Treatment compositions containing water-soluble polyelectrolyte complex which are self-limiting
US9663747B2 (en) 2010-03-29 2017-05-30 The Clorox Company Precursor polyelectrolyte complexes compositions comprising oxidants
US9796872B2 (en) 2010-03-29 2017-10-24 The Clorox Company Polyelectrolyte complexes
US9809790B2 (en) 2010-03-29 2017-11-07 The Clorox Company Self-limiting treatment compositions containing water-soluble polyelectrolyte complex
US10400131B2 (en) 2010-03-29 2019-09-03 The Clorox Company Polyelectrolyte complexes
US20110236450A1 (en) * 2010-03-29 2011-09-29 The Clorox Company Polyelectrolyte complexes
US20110236582A1 (en) * 2010-03-29 2011-09-29 Scheuing David R Polyelectrolyte Complexes
US10066196B2 (en) 2010-03-29 2018-09-04 The Clorox Company Polyelectrolyte complexes
US9895722B2 (en) 2012-08-31 2018-02-20 3M Innovative Properties Company Method of removing an unwanted constituent from a surface, a method of determining the cleanliness of a hard surface, and a multi-functional composition that includes hydrophilic silane
US10654078B2 (en) 2012-08-31 2020-05-19 3M Innovative Properties Company Method of removing an unwanted constituent from a surface, a method of determining the cleanliness of a hard surface, and a multi-functional composition that includes hydrophilic silane
US9518245B2 (en) 2013-12-16 2016-12-13 3M Innovative Properties Company Detergent and rinse-aid compositions containing a zwitterionic sulfonated silane and methods of using
EP2896637A1 (en) * 2014-01-21 2015-07-22 Rhodia Operations Copolymer comprising units of type A deriving from carboxylic acid monomers and units of type B deriving from sulfonic acid monomers
US11384315B2 (en) 2014-01-21 2022-07-12 Rhodia Operations Copolymer comprising units of type a deriving from carboxylic acid monomers and units of type b deriving from sulfonic acid monomers
WO2015110956A1 (en) * 2014-01-21 2015-07-30 Rhodia Operations Copolymer comprising units of type a deriving from carboxylic acid monomers and units of type b deriving from sulfonic acid monomers
US11000619B2 (en) 2014-03-28 2021-05-11 S. C. Johnson & Son, Inc. Pump concentrated air freshener
US9045719B1 (en) 2014-08-11 2015-06-02 The Clorox Company Hypohalite compositions comprising a diallyl dimethyl ammonium chloride polymer
US8975220B1 (en) 2014-08-11 2015-03-10 The Clorox Company Hypohalite compositions comprising a cationic polymer
US11130933B2 (en) 2016-01-20 2021-09-28 Rockline Industries, Inc. Wet wipes containing hydroxy acetophenone and cocamidopropyl PG dimonium chloride phosphate
US20180100123A1 (en) * 2016-10-12 2018-04-12 Mectra Labs, Inc. Cleaning solution
US10980230B2 (en) 2018-04-09 2021-04-20 Rhodia Operations Compositions and methods for long lasting disinfection
CN112203513A (en) * 2018-04-09 2021-01-08 罗地亚经营管理公司 Compositions and methods for durable disinfection
WO2019199886A1 (en) * 2018-04-09 2019-10-17 Rhodia Operations Compositions and methods for long lasting disinfection
US11877575B2 (en) 2018-04-09 2024-01-23 Rhodia Operations Compositions and methods for long lasting disinfection
EP4464159A3 (en) * 2018-04-09 2025-02-26 Specialty Operations France Compositions and methods for long lasting disinfection
WO2020168046A1 (en) * 2019-02-13 2020-08-20 Rhodia Operations Long lasting disinfectant cleaning compositions and methods of use thereof

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WO2004092316A1 (en) 2004-10-28
JP2007525549A (en) 2007-09-06

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