JP2007525549A - Use of sulfonated polystyrene polymers in hard surface cleaners to provide an easy cleaning effect - Google Patents

Abstract

  The aqueous hard surface cleaner composition is a surfactant selected from the group consisting of a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, a zwitterionic surfactant, and a mixture thereof; If the surfactant comprises a quaternary ammonium surfactant, the hydrophilic polymer comprising styrene sulfonate repeat units, which may be absent, and water, exhibiting a pH of about 6 or more, and easier Provides a clean effect.

Description

The present invention relates to the use of sulfonated polystyrene polymers in hard surface cleaners.

BACKGROUND OF THE INVENTION Hard surface cleaners typically include a nonionic surfactant, an antibacterial agent (which can be a quaternary ammonium type surfactant), a chelating agent, a solvent and water. Optionally, an anionic surfactant may be used if the antibacterial agent is eliminated or replaced with something other than a quaternary ammonium type surfactant. The most common surfactant systems for household cleaners are alkyl polyglucosides or alkyl ethoxylates.

  The hard surface cleaner is formulated to provide a cleaning effect with little or no air bubbles and to dry very rapidly with little or no streaking or residue. Surfactants and solvents provide most of the cleaning effect, and the surfactant may leave some residual hydrophilizing effect on the surface. Hydrophilization can improve ease of cleaning by tending to prevent hydrophobic contaminants from adhering to the surface. However, the surfactant can be easily washed off when rinsing or wiping, so the ease of cleaning effect is short if present. This is especially true for hydrophobic surfaces. A hydrophilic surface inherently repels hydrophobic contaminants to some extent. A less polar or nonpolar surface, however, does not naturally have the property of avoiding contaminants that are normally hydrophobic.

SUMMARY OF THE INVENTION In one aspect, the present invention provides:
A surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof,
Disinfectant, but may be absent if the surfactant comprises a quaternary ammonium surfactant,
A hydrophilic polymer comprising styrene sulfonate repeating units, and
water,
And an aqueous hard surface cleaner composition having a pH of about 6 or higher.

  In another aspect, the present invention relates to a method for cleaning a hard surface comprising contacting the aqueous hard surface cleaner described above with a hard surface.

  The composition of the present invention provides an easier cleaning effect, which is easier to remove contaminants from surfaces cleaned with the hard surface cleaner composition of the present invention prior to fouling. Before being soiled, by comparing it with the ease of removing contaminants from a surface cleaned with a hard surface cleaner similar to the hard surface cleaner composition of the present invention but which does not contain a hydrophilic polymer component. The

Detailed Description and Preferred Embodiments Suitable hard surfaces are smooth, substantially non-porous surfaces, including, for example, glass, ceramics, organic polymers, metals or wood.

In one embodiment, the hard surface cleaner composition of the present invention is based on 100 parts by weight (pbw) of such a composition.
From about 0.01 to about 10 pbw, more usually from about 0.01 to about 5 pbw of surfactant,
An amount of fungicide effective as a fungicide,
From about 0.01 to about 10 pbw, more usually from about 0.01 to about 3 pbw of a hydrophilic polymer, and
water,
including.

  Nonionic surfactants are surfactant compounds that do not dissociate into ions and do not have a bound charge. Suitable nonionic surfactants are generally known in the art and are prepared, for example, by condensation of alkylene oxide groups (hydrophilic) with organic hydrophobic compounds which can be aliphatic or alkylaromatic. A compound. Examples of useful nonionic surfactants include polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols, fatty acid amide surfactants, polyhydroxy fatty acid amide surfactants, amine oxide surfactants, alkyl ethoxylate surfactants, Alkanoyl glucose amide surfactants, alkanolamide surfactants, alkyl polyglycosides, and condensation products of aliphatic alcohols with from about 1 mole 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, alkylamine oxides such as lauramine oxide, cocamine Oxides, 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 acids Esters such as lauric acid, isostearic acid and PEG-150 distearate, fatty alcohols or ethoxylated fatty alcohols, and Lauryl alcohol, laureth-4, laureth-7, laureth-9, laureth-40, trideceth alcohol, C11-C15 Palace-9, C12-C13 Palace-3 and C14-C15 Palace-11, and their Contains a mixture.

  Cationic surfactants are ionic surfactant compounds having a positive charge attached to the hydrophilic portion of the surfactant. Suitable cationic surfactants are generally known in the art and include, for example, compounds according to the following formula (1):

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen or 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, ethosulphate, lactate, saccharinate, acetate or phosphate.

If R _1, R _2, R ₃ and one to 3 one of R ₄ groups are hydrogen, the compound may be referred to as an amine salt. Some examples of cationic amine salts include polyethoxylated (2) oleyl / stearylamine, ethoxylated tallow amine, cocoalkylamine, oleylamine and tallow alkylamine, and mixtures thereof.

In quaternary ammonium compounds (commonly referred to as “quaternary” (quats)), R ₁ , R ₂ , R ₃ and R ₄ can each independently be the same or different organic groups. Or may be condensed with another R ₁ , R ₂ , R ₃ and R ₄ group to form a heterocycle with the nitrogen to which they are attached, but should 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 monoalkylamine derivatives, dialkylamine derivatives and imidazoline derivatives, and mixtures thereof.

  Suitable monoalkylamine derivatives include, for example, cetyltrimethylammonium bromide (also known as cetrimonium bromide or CETAB), cetyltrimethylammonium chloride (also known as cetrimonium chloride), myristyltrimethylammonium bromide (mil Trimonium chloride or Quaternium-13), stearyldimethylbenzylammonium chloride (also known as stearalkonium chloride), oleyldimethylbenzylammonium chloride (also known as olealkonium chloride) Lauryl / myristoltrimethylammonium methosulfate (also known as cocotrimonium methosulfate), cetyl-dimethyl- (2) hydride Roxyethylammonium dihydrogen phosphate (also known as hydroxyethyl cetyldimonium phosphate), basamidopropylconium chloride, cocotrimonium chloride, distearyl dimonium chloride, wheat embryo amide propalconium chloride, stearyl octyl di Monium methosulfate, isostearaminoproparconium chloride, dihydroxypropyl PEG-5 linoleaminium chloride, PEG-2 stearmonium chloride, Quaternium 18, Quaternium 80, Quaternium 82, Quaternium 84, behentrimonium chloride, di Cetyldimonium chloride, behentrimonium methosulfate, tallow trimonium chloride, and behenamidopropylethyldimonium etosulphate, and their A mixture of

  Suitable dialkylamine derivatives are, for example, distearyl dimonium chloride, dicetyl dimonium chloride, stearyl octyl dimonium methosulfate, dihydrogenated palmoylethylhydroxyethylmonium methosulfate, dipalmitoylethylhydroxyethylmonium methosulfate. Fate, dioleoylethyl hydroxyethylmonium methosulfate, hydroxypropyl bisstearyl dimonium chloride, and mixtures thereof.

  Suitable imidazoline derivatives include, for example, isostearyl benzyliminium chloride, cocoyl benzylhydroxyethyl imidazolinium chloride, cocoyl hydroxyethyl imidazolinium PG-chloride phosphate, Quaternium-32, and stearyl hydroxyethylimidonium chloride, and Including mixtures thereof.

  An amphoteric surfactant is an ionic surfactant compound characterized by the presence of two ionic sites on the same molecule, depending on the pH of the surrounding medium, negative charge, positive charge or both negative and positive charge are the same. Can have on the molecule. Suitable amphoteric surfactants are known in the art, for example, derivatives of aliphatic secondary and tertiary amines, where the aliphatic group may be linear or branched, saturated or unsaturated. Which may be saturated, one of the aliphatic substituents containing from about 8 to about 22 carbon atoms and one containing an anionic water solubilizing group. Specific examples of suitable amphoteric surfactants include alkyl amphocarboxyglycinate and alkylamphocarboxypropionate, alkylamphodipropionate, alkylamphodiacetate, alkylamphoglycinate and alkylamphopropionate. As well as alkali metal, alkaline earth metal, ammonium or substituted ammonium salts of alkyliminopropionate, alkyliminodipropionate and alkylamphopropylsulfonate. Amphoteric surfactants are usually bound to a counter ion such as sodium, magnesium, potassium, ammonium or substituted ammonium cations. Specific examples of some suitable amphoteric surfactants include sodium cocoamphoacetate, sodium cocoamphopropionate, disodium cocoamphodiacetate, diammonium cocoamphophone diacetate, sodium lauroamphoacetate, Disodium Lauroamphodiacetate, Dipotassium Lauroamphodiacetate, Dimagnesium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Cocoamphopropyl Sulfonate Caproamphodiacetate, Sodium Caproan Phoacetate, disodium caproamphodipropionate, sodium stearoamphoacetate, triethanolamine stearoamphoacetate, and mixtures thereof Including things.

  Zwitterionic surfactants are per molecule where one ionic site can have a positive charge regardless of the pH of the surrounding medium and the other ionic site can have a positive charge depending on the pH of the surrounding medium. Are ionic surface active compounds characterized by the presence of two ionic sites. Suitable zwitterionic surfactants are generally known in the art, for example, derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, where the aliphatic group may be linear or branched. May be saturated or unsaturated, one of the aliphatic substituents containing from about 8 to about 22 carbon atoms, one of which is an anionic water solubilizing group such as carboxyl, sulfonate, sulfate, phosphate or Including those that can be broadly described as including phosphonates. Specific examples of suitable zwitterionic surfactants include alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine, lauryldimethylα-carboxyethylbetaine, cetyldimethylcarboxymethylbetaine, laurylbis- (2- Hydroxyethyl) carboxymethyl betaine, stearyl bis (2-hydroxypropyl) carboxymethyl betaine, oleyldimethyl γ-carboxypropyl betaine, lauryl bis (2-hydroxypropyl) α-carboxyethyl betaine, amidopropyl betaine and alkyl sultain, for example Cocodimethylsulfopropylbetaine, stearyldimethylsulfopropylbetaine, lauryldimethylsulfoethylbetaine, laurylbis (2 Hydroxyethyl) sulfopropyl betaine and alkyl amidopropyl hydroxysultaines, and mixtures thereof.

  The disinfectant component of the hard surface cleaner of the present invention is any compound that exhibits bactericidal activity on the hard surface to which the hard surface cleaner of the present invention is applied, i.e., can kill bacteria and / or inhibit bacterial growth. For example, including sodium hypochlorite and quaternary ammonium compounds.

  A sterilizing effective amount of the quaternary ammonium compound is typically about 0.01 to about 10 pbw, more usually about 0.01 to about 3 pbw of the fourth quaternary per 100 pbw of the hard surface cleaner composition of the present invention. It is a quaternary ammonium compound.

  Quaternary ammonium compounds suitable for use as the bactericide 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 contains at least an effective amount of a quaternary ammonium surfactant as a fungicide, such a quaternary ammonium surfactant also functions as a fungicide. In this case, a separate fungicide is not necessary.

  In one embodiment, the primary surfactant is selected from semipolar nonionic surfactants, alkylbetaines 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, such as (C ₁ -C ₆ ) alkanols, (C ₁ -C ₆ ) diols, (C ₃ -C ₂₄ ) alkylene glycol ethers and mixtures thereof. including. In one embodiment, the composition of the present invention further comprises about 10 pbw or less 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 known in the art and include, for example, aminophosphonate chelating agents and ethylenediaminetetraacetic acid. Suitable aminophosphonate chelating agents include, for example, ethylenediaminetetramethylenephosphonate, diethylenetriaminepentamethylenephosphonate. In one embodiment, the chelating agent comprises ethylenediaminetetraacetic acid. In one embodiment, the composition of the present invention comprises from about 0.01 to about 10 pbw, more usually from about 0.1 to about 3 pbw of a chelating agent, based on 100 pbw of the hard surface cleaner composition of the present invention. .

The hydrophilic polymer of the present invention may be any polymer containing styrene sulfonate repeat units, including styrene sulfonate homopolymers, such as poly (sodium 4-styrene sulfonate) polymers, as well as styrene sulfonate repeat units, which repeat units. Includes copolymers copolymerized with repeat units derived from one or more other monoethylenically unsaturated monomers. Suitable ethylenically unsaturated monomers are, for example, styrene, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, vinyl acetate, maleic acid, fumaric acid, acrylic acid or methacrylic acid (C ₁ ~C ₄₎ alkyl esters, for example, including methyl acrylate and methyl methacrylate, (C ₁ ~C ₄₎ hydroxyalkyl esters of acrylic or methacrylic acid, for example, hydroxyethyl methacrylate. Suitable copolymers include random copolymers, graft copolymers and block copolymers such as poly (styrene sulfonic acid-co-maleic acid) sodium salt, poly (sodium 4-styrene sulfonate) -poly (styrene) random copolymer, poly (sodium 4 Styrene sulfonate) -b-poly (acrylamide) block copolymer, poly (sodium 4-styrene sulfonate) -b-poly (styrene) block copolymer, poly (sodium 4-styrene sulfonate) -b-poly (hydroxyethyl methacrylate) block Copolymers and poly (sodium 4-styrenesulfonate) -b-poly (methacrylic acid) block copolymers.

  In one embodiment, suitable copolymers include, on average, about 1 mole or more of styrene sulfonate repeat units per 100 moles of repeat units of the copolymer. In embodiments where the comonomer of such a copolymer is a hydrophobic comonomer, such as styrene, such a copolymer is typically on average about 20 moles or more, more usually 40 moles or more per 100 moles of repeating units of the copolymer. Of styrene sulfonate repeat units.

  In one embodiment, the hydrophilic polymer is about 1000 or greater, more usually about 5000 to about 5,000,000, and even more usually about 10, as determined by gel permeation chromatography (GPC). A weight average molecular weight (Mw) of 000 to about 2,000,000 is indicated.

  In one embodiment, the hard surface cleaner composition of the present invention exhibits a pH of about 7 to about 14, more usually about 7 to about 13, and even more usually about 8 to about 13. .

  The hard surface cleaner composition of the present invention may optionally contain other components up to about 10 pbw per 100 pbw of the hard surface cleaner composition, such as perfumes, colorants, opacifiers, bleaches, pH adjusters, detergent enzymes , Stabilizers, bactericidal active ingredients, thickeners, hydrotropes.

  The hard surface cleaning composition of the present invention is made by combining and mixing the desired and appropriate relative amounts of the above components.

  In one embodiment of the method of the present invention, the hard surface is contacted with the hard surface cleaning composition of the present invention, and the hard surface cleaning composition and the surface are rinsed or wiped with water and dried.

  The use of a hard surface cleaner to clean the hard surface makes it easier to clean the surface in subsequent cleaning activities. While not intending to be bound by theory, some of the hydrophilic polymer component of the cleaner composition remains on the surface after cleaning and inhibits surface interactions with hydrophobic contaminants that would later contact the surface, thereby It is believed that it will be easier to remove contaminants from the surface.

Examples 1-10 and Comparative Examples C1 and C2
The easier cleaning effect afforded by treating a hard surface with a polymer containing styrene sulfonate repeat units is to treat the surface of the Formica laminate tile with such a polymer, contaminate the surface, and then rub the surface and rub. It was measured by grading the degree of cleanliness of the resulting surface.

  A scrub test device was used. The scrub test apparatus is a wooden panel (approximately 40 cm long) with rails holding 8 sample tiles in one row, and a metal track with rails guiding a sponge holder placed on the panel to wipe the tiles It consisted of.

  A Formula 409 (antibacterial formulation) general purpose cleaner was used as Comparative Example C1, and a Fantastik general purpose cleaner was used as Comparative Example C2. The Formula 409 cleaner exhibited a pH of about 12.3. The fantastic cleaner exhibited a pH of about 12.2.

  The cleaner compositions of Examples 1-10 each contain 1 wt% hydrophilic polymer and the hydrophilic polymers shown in Table I below are added to Formula 409 (antibacterial formulation) universal cleaner (Clorox). It was manufactured by. The pH of each composition of Examples 1-10 was adjusted to a value of 12.3 ± 0.1.

  By adding 0.1 mL of ethanol to the surface of the base tile (5 cm x 5 cm white Formica ™ laminated square body attached to a 1.3 cm thick particle board) Pre-cleaned and wiped with a paper towel. The tile was allowed to dry at room temperature for at least 30 minutes.

  The substrate tile was processed as follows. 1.0 mL of the treatment formulation shown in the table below was pipetted onto the precleaned surface. The formulation was spread throughout the top surface of the tile and left on the surface of the tile for 5 minutes. The top surface of the tile was then wiped three times with each side of a 4 cm × 4 cm cellulose sponge wetted with water and allowed to dry at room temperature for 2-3 hours.

  Test contaminants were made by combining 20.0 g of curing agent and 90 g of contaminant material and mixing it for 4-5 hours. The contaminated material was prepared by mixing 60 g sunflower oil, 10 g olive oil and 20 g iron oxide pigment in a 150 ml plastic beaker with a stir bar at room temperature for about 30 minutes. The curing agent was prepared by mixing 45 g isooctane and 1 g cobalt naphthenate in a 150 ml plastic beaker with a stir bar at room temperature for about 30 minutes.

  A lightly contaminated substrate tile was prepared as follows. Eight tiles were attached to the scrub test apparatus. A 4 inch wide soft rubber ink roller was wetted with test contaminants. A drop of test contaminant was applied to the third and fifth tiles and the drops were spread evenly over the four inner tiles using a wet roller. The tiles were placed in a constant temperature and humidity chamber (25 ° C., 50% RH) for 24 hours.

  A heavily contaminated substrate tile was prepared as follows. Eight tiles were attached to the scrub test apparatus. A drop of test contaminant was deposited on the third and fifth tiles and the droplet was spread evenly over the four inner tiles using a 4 inch wide soft rubber ink roller wetted with contaminants. . A drop of test contaminant was deposited on the second and fourth tiles and the droplet was spread evenly on the four inner tiles using a roller wetted with contaminants. The tiles were placed in a constant temperature and humidity chamber (25 ° C., 50% RH) for 24 hours.

  The contaminated substrate tile was rubbed. Eight tiles were attached to the scrub test apparatus. In each case, the four inner tiles were the test sample of interest and the outer tile was just a placement support. A 4 cm × 9 cm cellulose sponge was rinsed in water and removed by hand so that it was wet but not so wet as to drip. The sponge was placed in a metal sponge holder. The cleaner was sprayed for several minutes to obtain a consistent deep spray for testing. The first two contaminated tiles were sprayed once (about 1.3 g) with a cleaner from about 4 inches away. The second two contaminated tiles were then immediately sprayed once with a cleaner from about 4 inches away. The sponge in the metal holder was placed on the track, moved 10 times from one end of the track to the other end (once from one end of the track to the other end) and rubbed the scrub tester tile. The inner tile was removed from the scrub test apparatus, examined, and graded with a decontamination grade 0-5 (0 is no removal and 5 is complete removal). The results are shown in Table I below. Each grade is based on an average of 8 cleaned tiles.

Example 11
The components shown in Table II below are combined in relative amounts shown in Table II below to produce a hard surface cleaner composition.

Claims (10)

A surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof,
Disinfectant, but may be absent if the surfactant comprises a quaternary ammonium surfactant,
A hydrophilic polymer comprising styrene sulfonate repeating units, and
An aqueous hard surface cleaner composition comprising water and exhibiting a pH of about 6 or greater.   The composition comprises from about 0.01 to about 10 parts by weight primary surfactant, from about 0.01 to about 10 parts by weight bactericidal agent, and from about 0.01 to about 10 parts by weight, based on 100 parts by weight of the composition. The composition of claim 1 comprising 1 part by weight of a hydrophilic polymer.   The composition of claim 1, wherein the primary surfactant comprises a nonionic surfactant.   The composition of claim 1, wherein the fungicide comprises one or more quaternary ammonium surfactants.   The composition of claim 1, wherein the hydrophilic polymer is a homopolymer of parastyrene sulfonate.   The hydrophilic polymer is a copolymer of parastyrene sulfonate and a monomer selected from the group consisting of maleic acid or a salt or anhydride thereof, acrylamide, styrene, polyethylene glycol, hydroxyethyl methacrylate and methacrylic acid or a salt thereof. Item 2. The composition according to Item 1.   The hydrophilic polymer is poly (sodium 4-styrene sulfonate), poly (styrene sulfonic acid-co-maleic acid) sodium salt, poly (sodium 4-styrene sulfonate) -poly (styrene) random copolymer, poly (sodium 4-styrene sulfonate). Sulfonate) -b-poly (acrylamide) block copolymer, poly (sodium 4-styrene sulfonate) -b-poly (styrene) block copolymer, poly (sodium 4-styrene sulfonate) -b-poly (hydroxyethyl methacrylate) block copolymer and The composition of claim 1 comprising at least one polymer selected from poly (sodium 4-styrenesulfonate) -b-poly (methacrylic acid) block copolymers.   The composition according to claim 1, further comprising a water-soluble organic solvent.   The composition of claim 1 further comprising a chelating agent.   A method for cleaning a hard surface comprising contacting the hard surface with an aqueous hard surface cleaner according to claim 1.