WO1996030474A1 - Use of amine oxide surfactants for improved stain removal performance - Google Patents

Use of amine oxide surfactants for improved stain removal performance Download PDF

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Publication number
WO1996030474A1
WO1996030474A1 PCT/US1996/003977 US9603977W WO9630474A1 WO 1996030474 A1 WO1996030474 A1 WO 1996030474A1 US 9603977 W US9603977 W US 9603977W WO 9630474 A1 WO9630474 A1 WO 9630474A1
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WO
WIPO (PCT)
Prior art keywords
composition
caφet
amine oxide
compositions
cleaning
Prior art date
Application number
PCT/US1996/003977
Other languages
French (fr)
Inventor
Floriana Raso
Stefano Scialla
Raffaele Scoccianti
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP95203330A external-priority patent/EP0735133B1/en
Priority claimed from EP96870023A external-priority patent/EP0735131A3/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Publication of WO1996030474A1 publication Critical patent/WO1996030474A1/en

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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • C11D1/75—Amino oxides
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0031—Carpet, upholstery, fur or leather cleansers

Definitions

  • the present invention relates to the use of amine oxide surfactants in cleaning compositions and more particularly to their ability to remove stains, soils or combinations thereof from carpets and fabrics.
  • Carpets produced from synthetic or natural fibers and mixtures thereof are commonly used in residential and commercial applications as a floor covering.
  • Various types of fibers can be used in making ca ⁇ ets such as polyamide fibers, polyester fibers as well as wool, cotton or even silk.
  • carpets as well as fabrics are all prone to soiling and staining when contacted with many household items.
  • Foods, grease, oils, beverages in particular such as coffee, tea and soft drinks especially those containing acidic dyes can cause unsightly, often dark stains on ca ⁇ ets and fabrics.
  • ca ⁇ et fibers may become soiled as a result of dirt particles, clay, dust, particulate soils in general, coming into contact with and adhering to the fibers of the ca ⁇ ets.
  • These latter soils often appear in the form of a diffuse layer of soils rather than in the form of spots and tend to accumulate particularly in the so called "high traffic areas" such as near doors as a result of intensive use of the carpets in such areas.
  • ca ⁇ et cleaning compositions described in the art for removing stains and soils from ca ⁇ ets As well as a number of fabric cleaning compositions described in the art for removing stains and soils from fabrics.
  • these compositions do not satisfactorily meet the consumer's needs regarding their cleaning performance on different types of stains and soils.
  • ca ⁇ et cleaning compositions are not fully satisfactory on removing particulate stains and/or greasy stains, especially in the so called "high traffic areas" of ca ⁇ ets.
  • the object of the present invention is to provide improved stain removal performance, in a manner which is applicable to a variety of cleaning compositions, i.e. compositions being either in a liquid form, or in a powder form, or in a granular form, and to a variety of applications like ca ⁇ ets and/or fabrics cleaning applications.
  • amine oxide surfactants according to the formula R1R2R3NO, wherein each of R1 , R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, in a cleaning composition.
  • said amine oxide surfactants allow to deliver improved stain removal performance on a variety of stains including particulate stains, greasy/oily stains like chocolate, sphagetti sauce, mayonnaise as well as bleachable stains like coffee, tea, and enzymatic stains like blood.
  • the present finding is applicable both in laundry cleaning application, especially in laundry pretreatment, and in carpet cleaning application.
  • An advantage of the present invention is that it is applicable to all ca ⁇ et types, especially delicate natural fibers and is also safe to all ca ⁇ et dye types, particularly sensitive natural dyes used therein.
  • the present invention is particularly suitable for the cleaning of upholstery and car seat coverings.
  • compositions to be used according to the present invention may be applied directly on the ca ⁇ et without causing damage to the ca ⁇ et.
  • cleaning action of the invention commences as soon as the ca ⁇ et cleaning composition has been applied to the surface.
  • the use of the ca ⁇ t cleaning compositions of the present invention does not necessarily require rubbing and/or brushing of the carpet.
  • a further advantage of the present invention is that it is applicable to all types of fabrics, especially delicate fabrics upon pretreatment conditions, e.g., when applied onto the fabrics even for a prolonged period of contact, before said fabrics are washed.
  • the present invention encompasses the use of an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of R1 , R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, in a cleaning composition, to improve the stain removal performance of said composition.
  • the present invention further encompasses a method of cleaning a carpet wherein a composition comprising an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, is applied to said ca ⁇ et, wherein said carpet is then optionally rubbed and/or brushed, and wherein said composition rs then removed from said ca ⁇ et.
  • a composition comprising an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms
  • the present invention also encompasses a method of pretreating fabrics with a composition comprising an amine oxide surfactant according to the formula R1R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, said method comprising the steps of applying said composition in its neat form onto the fabric, and allowing said composition to remain in contact with said fabric before said fabric is washed.
  • a composition comprising an amine oxide surfactant according to the formula R1R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms
  • the present invention relates to the use of amine oxide surfactants according to the formula R1R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, in a cleaning composition to improve the stain removal performance of said composition.
  • compositions to be used according to the present invention comprise an amine oxide surfactant or mixtures thereof.
  • Suitable amine oxide surfactants to be used herein are according to the following formula R1 R2R3NO wherein each of R1 , R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl groups of from 1 to 30 carbon atoms, and preferably of from 1 to 20 carbon atoms.
  • Particularly preferred amine oxide surfactants to be used according to the present invention are amine oxide surfactants having the following formula R1R2R3NO wherein R1 is a saturated linear or branched alkyl group of 1 to 30 alkyl group, preferably of 6 to 18 alkyl group, more preferably of 6 to 14, most preferably of 6 to 10 and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms, and more preferably are methyl groups.
  • R1 is a saturated linear or branched alkyl group of 1 to 30 alkyl group, preferably of 6 to 18 alkyl group, more preferably of 6 to 14, most preferably of 6 to 10 and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms, and more preferably are
  • said amine oxide surfactants are pure-cut amine oxide surfactants, i.e., a pure single amine oxide surfactant, e.g. C ⁇ N,N- imethyl amine oxide, as opposed to mixtures of amine oxide surfactants of different chain lenghts.
  • Suitable amine oxide surfactants for use herein are for instance pure cut C8 amine oxide or pure cut C10 amine oxide or pure cut C14 amine oxide, natural blend C8-C10 amine oxides as well as C12-C16 amine oxides.
  • Said amine oxide surfactants may be commercially available from Hoechst or Stephan.
  • said amine oxide surfactants allow to deliver improved stain removal performance on a variety of stains/soils including particulate stains, greasy/oily stains, bleachable stains and/or enzymatic stains.
  • stains in particular particulate stains and/or greasy/oily stains and/or bleachable stains and/or enzymatic stains achieved by using a cleaning composition comprising said amine oxide surfactants
  • a cleaning composition comprising said amine oxide surfactants
  • another surfactant like for instance alkyl sulphate instead of said amine oxide surfactants.
  • articulate stains it is meant herein any soils or stains of particulate nature that can be found on ca ⁇ ets or fabrics, e.g., clay, dirt, dust, mud, concrete and the like.
  • greasy/oily stains any soils or stains of greasy/oily nature that can be found on ca ⁇ ets or fabrics, e.g., make-up, lipstick, dirty motor oil and mineral oil, greasy food like mayonnaise and spaghetti sauce.
  • bleachable stains any stains on ca ⁇ ets or fabrics that can be oxidised by bleach, e.g. coffee, tea, wine, grass or fruit juice.
  • enzymatic stains any soils or stains of enzymatic nature that can be found on carpets or fabrics, e.g., blood.
  • compositions herein further comprise a source of active oxygen
  • the presence of said amine oxide surfactants improves the chemical stability of said compositions. Indeed, we have observed that improved chemical stability, i.e., lower decomposition of the bleach and the bleach activator, if present, is obtained by adding such an amine oxide surfactant. It is believed that such stability is due to the capacity of the amine-oxide surfactants to limit interactions between the bleach and the bleach activator, if present, possibly through emulsification. It is believed that this stabilising effect is matrix independent.
  • said amine oxide surfactants especially pure-cut short chain (C6-C10) amine oxide surfactants have the advantage to reduce the amount of residues left onto fibers being treated with a composition comprising them. Also, the residues left after said composition comprising them has performed its cleaning action are partially in a crystalline form. Indeed, it has been observed that with the compositions according to the present invention comprising said amine oxide surfactants, especially pure-cut amine oxide surfactants, more than 90%, preferably more than 95%, of the residues left onto the fibers are crystals (generally lamellar and/or needle- shaped) with an average particle surface bigger than 300 ⁇ 2 .
  • an advantage of the finding of the present invention is that it is applicable in different cleaning processes including ca ⁇ et cleaning and fabric cleaning especially fabric pretreatment.
  • such cleaning compositions comprising said amine oxide surfactants are particularly useful as laundry pretreaters, i.e. in a process where said composition is applied in neat form onto soiled portions of fabrics before said fabrics are washed in a separate, typical laundry operation.
  • said composition in neat form is left to act on said portions for a period of time before the fabrics are washed in said laundry operation.
  • said composition in neat form is not left to dry onto said portions.
  • said period of time is in between 1 minute to several hours, more preferably 1 minute to 1 hour, more preferably 1 minute to 30 minutes and most preferably 2 to 10 minutes.
  • said pretreatment process may additionally involve rubbing and scrubbing. It has been observed that in such a pretreatment process, the presence of said amine oxide surfactants improves the stain removal performance on a variety of stains. It is believed that this improvement in stain removal performance is matrix independent.
  • Such cleaning compositions comprising said amine oxide surfactants are also particularly useful as ca ⁇ et cleaning compositions.
  • the present invention also encompasses a method of cleaning a ca ⁇ et wherein a composition comprising an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, is applied to said carpet, wherein said ca ⁇ et is then optionally rubbed and or brushed, and wherein said composition is then removed from said ca ⁇ et.
  • the step of applying a composition for the cleaning of ca ⁇ ets as described herein before may be followed by a rubbing step and/or a brushing step.
  • An advantage of the present invention is that the cleaning action of said compositions commences as soon as said compositions are applied onto said ca ⁇ et.
  • the cleaning process of the present invention does not necessarily require rubbing and/or brushing.
  • the carpet may be cleaned by applying onto it said composition for the cleaning of carpets according to the present invention, then rubbing and/or brushing it more or less intensively for example by means of a sponge or a brush or other mechanical/electrical device, optionally with the aid of water.
  • the rubbing/brushing-times are between 1 to a few minutes per square meter.
  • compositions for the cleaning of ca ⁇ ets according to the present invention may be applied to the ca ⁇ et to be cleaned either in neat or diluted form, this applies to compositions being either liquid compositions or granular compositions or powder compositions.
  • compositions for the cleaning of carpets according to the present invention may be diluted by the user, preferably with water.
  • Said compositions can be diluted up to 150 times, preferably up to 50 times and more preferably up to 25 times.
  • the compositions for the cleaning of ca ⁇ ets according to the present invention are liquid aqueous compositions.
  • a liquid aqueous composition i.e. an aqueous composition for the cleaning of ca ⁇ ets in its neat form or which has been diluted with water by the user or an aqueous composition resulting from the dilution of a granular composition or of a powder composition, is applied to the ca ⁇ et to be cleaned, said ca ⁇ et is optionally rubbed and/or brushed, then said composition is left to dry and then removed from said ca ⁇ et.
  • said liquid aqueous composition is left to dry until said composition which combined with dirt has been changed into dry residues.
  • liquid aqueous compositions may be applied directly onto the area to be treated or applied using a cloth or piece of material such as spraying device or aerosol can, a sponge, a brush or other mechanical/electrical device.
  • a liquid aqueous composition is applied to the area to be treated by using a spraying device or an aerosol can.
  • a spraying device may be trigger operated or pump operated or electrically operated or operated by any source of pressurised gas such as a can or a pressurizer.
  • Such spraying devices are particularly preferable if a large area is to be treated as it facilitates the ease of use for the consumer.
  • the spraying devices ensure uniform coverage of the area to be treated and maximises the advantage of the using liquid aqueous compositions containing peroxides. This is because the application of product by spray best allows the product to be left to dry on the area treated, even without rubbing or brushing. This optimises the action time of the composition and allows the best exploitation of the bleaching action of peroxides.
  • compositions for the cleaning of ca ⁇ ets according to the present invention are granular compositions or powder compositions.
  • Such compositions for the cleaning of ca ⁇ ets according to the present invention may be applied directly onto the area of the ca ⁇ et to be treated by for example sprinkling said composition over said area or may be applied by using a sponge, a brush, or other mechanical/electrical device preferably in presence of water and then left to dry and then removed from said ca ⁇ et.
  • the area to be treated using the compositions according to the present invention may be any size.
  • a complete section or even a whole ca ⁇ et may be applied with the composition for the cleaning of ca ⁇ ets according to the present invention.
  • a spraying device with a pump to allow prolonged spraying is particularly useful.
  • the amount of the compositions for the cleaning of ca ⁇ ets according to the present invention applied will depend on the severity of the stains or soils. In the case of stubborn stains more than one application may be required to ensure complete removal of the stain.
  • the ca ⁇ et cleaning compositions may also be used in order to deodorise the ca ⁇ et and remove the dinginess of the ca ⁇ et resulting from a diffused layer of soil which results from general wear.
  • compositions for the cleaning of ca ⁇ ets according to the present invention may be used both for manual ca ⁇ et cleaning and ca ⁇ t cleaning machines.
  • compositions for the cleaning of ca ⁇ ets according to the present invention i.e. either liquid compositions or granular compositions or powder compositions, may be preferably diluted according to the machine operating instructions.
  • compositions suitable to be used according to the present invention may be formulated either as solids or liquids.
  • the compositions may be formulated as solids for example as granular compositions or powder compositions, they may be applied directly on the surfaces to be treated or they may be diluted with an appropriate solvent, typically water, before use.
  • the compositions are preferably but not necessarily formulated as aqueous compositions. Liquid compositions are preferred herein for convenience of use.
  • compositions according to the present invention may further comprise as an optional but highly preferred ingredient a source of active oxygen or mixtures thereof.
  • said compositions are liquid aqueous compositions and have the advantage, due to the presence of said amine oxide surfactants, to be particularly efficient in terms of overall cleaning performance and to be chemically stable. Indeed, said liquid aqueous compositions according to the present invention do not require pH adjustment prior to use and can be stored for long periods of time prior to use.
  • a preferred source of active oxygen according to the present invention is hydrogen peroxide or sources thereof.
  • a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said .compound is in contact with water.
  • Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, metal peroxides and perborates.
  • peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof.
  • Suitable classes include dialkylperoxides, diacylperoxides, preformed percarboxylic acids, persilicates, persulphates, organic and inorganic peroxides.
  • Suitable organic and inorganic peroxides for use in the compositions according to the present invention include diacyl and dialkyl peroxides such as dibenzoyi peroxide, dilauroyl peroxide, dicumyl peroxide, persulphuric acid and mixtures thereof.
  • Suitable preformed peroxyacids for use in the compositions for the cleaning of ca ⁇ ets according to the present invention include diperoxydodecandioic acid DPDA, magnesium pe ⁇ hthalatic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
  • compositions suitable to be used according to the present invention comprise from 0.1% to 15%, preferably from 0.5% to 10%, more preferably from 1 % to 7% by weight of active oxygen in said compositions.
  • active oxygen concentration refers to the percentage concentration of elemental oxygen, with an oxidation number zero, that being reduced to water would be stoichiometrically equivalent to a given percentage concentration of a given peroxide compound, when the peroxide functionality of the peroxide compound is completely reduced to oxides.
  • the active oxygen sources according to the present invention increase the ability of the compositions to remove colored stains, to destroy malodorous molecules and to kill germs.
  • the concentration of available oxygen can be determined by methods known in the art, such as the iodimetric method, the permanganometric method and the cerimetric method. Said methods and the criteria for the choice of the appropriate method are described for example in "Hydrogen Peroxide", W. C. Schumb, C. N. Sat.er-f.eld and R. L. Wentworth, Reinhold Publishing Co ⁇ oration, New York, 1955 and "Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970.
  • the compositions suitable to be used according to the present invention may further comprise a bleach activator or mixtures thereof, as another optional ingredient.
  • bleach activator it is meant herein a compound which reacts with hydrogen peroxide to form a peracid.
  • the peracid thus formed constitutes the activated bleach.
  • Suitable bleach activators to be used herein include those belonging to the class of esters, amides, imides, or anhydrides. Examples of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231 and a method for their formation into a prilled form is described in European Published Patent Application EP-A-62 523.
  • Suitable examples of such compounds to be used herein are tetracetyl ethylene diamine (TAED), sodium 3,5,5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n- nonanoyloxybenzenesulphonate (NOBS).
  • TAED tetracetyl ethylene diamine
  • NOBS n- nonanoyloxybenzenesulphonate
  • N-acyl caprolactam selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam or mixtures thereof.
  • a particular family of bleach activators of interest was disclosed in EP 624 154, and particularly preferred in that family is acetyl triethyl citrate (ATC).
  • Acetyl triethyl citrate has the advantages that it is environmentally friendly as it eventually degrades into citric acid and alcohol. Furthermore, acetyl triethyl citrate has a good hydrolytical stability in the composition upon storage and it is an efficient bleach activator. As used herein and unless otherwise specified, the term bleach activator includes mixtures of bleach activators.
  • compositions suitable to be used according to the present invention may comprise up to 30% by weight of the total composition of said bleach activator, or mixtures thereof, preferably from 1% to 20%, and more preferably from 2% to 10%.
  • the pH of the liquid compositions suitable to be used according to the present invention can be from 0 to 14.
  • the recommended pH range to achieve good hydrogen peroxide stability is from 0 to 9, preferably between pH 0 and 8, more preferably between pH 0 and 7 and most preferably between 1 and 6.
  • the compositions herein may further comprise an acid to adjust pH.
  • some acids can have the advantage that they can form small concentrations of the corresponding peracids by reaction with hydrogen peroxide in-situ, thus enhancing the overall performance of the composition. These acids can be further selected so as to have chelating and/or building properties.
  • the acids of the present invention that may be used for these purposes can be organic or inorganic acids, preferably organic acids such as citric, maleic, oxalic succinic, and tartaric acids or inorganic acids such as sulphuric acid.
  • composition suitable to be used according to the present invention may comprise various optional ingredients depending on its end use as a laundry cleaning composition or as a ca ⁇ et cleaning composition.
  • compositions suitable to be used according to the present invention may comprise a chelating agent or mixtures thereof, as a highly preferred optional ingredient.
  • Chelating agents suitable to be used herein include chelating agents selected from the group of phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, and further chelating agents like glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof.
  • Suitable phosphonate chelating agents to be used herein may include ethydronic acid as well as amino phosphonate compounds, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates.
  • the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
  • Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonates.
  • Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®- Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy -3,5-disulfobenzene.
  • a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
  • Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
  • Ethylenediamine N,N'- disuccinic acids are, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
  • Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA).N- hydroxyethylethylenediamine triacetates, nitrilotri- acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa- acetates, ethanoldiglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Triton FS® and methyl glycine di-acetic acid (MGDA).
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Particularly preferred chelating agents to be used herein are diethylene triamine methylene phosphonate, ethylene N.N'-disuccinic acid, diethylene triamine pantaacetate, glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid or mixtures thereof and highly preferred is salicylic acid.
  • Salicylic acid may be commercially available from Rhone-Poulenc under the name Salicylic Acid®.
  • compositions suitable to be used according to the present invention comprise up to 5% by weight of the total composition of said chelating agent or mixtures thereof, preferably from 0.1% to 4% and more preferably from 0.1 % to 2%.
  • compositions suitable to be used herein may also comprise soil suspending polycarboxylate polymers.
  • soil suspending polycarboxylate polymer known to those skilled in the art can be used according to the present invention such as homo- or co-polymeric polycarboxylic acids or their salts including polyacrylates and copolymers of maleic anhydride or/and acrylic acid and the like.
  • soil suspending polycarboxylate polymers can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates to be used herein can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred soil suspending polycarboxylic polymer.
  • Such materials include the water- soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982. Particularly preferred is a copolymer of maleic / acrylic acid with an average molecular weight of about 70,000. Such copolymers are commercially available from BASF under the trade name SOKALAN CP5.
  • compositions suitable to be used herein may also comprise soil suspending polyamine polymers as optional ingredients.
  • soil suspending polyamine polymer known to those skilled in the art may also be used herein.
  • Particularly suitable polyamine polymers for use herein are polyalkoxylated polyamines. Such materials can conveniently be represented as molecules of the empirical structures with repeating units :
  • R is a hydrocarbyl group, usually of 2-6 carbon atoms;
  • R 1 may be a C1-C20 hydrocarbon;
  • the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most preferably from 10-20;
  • n is an integer of at least 2, preferably from 2-20, most preferably 3-5;
  • X * is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
  • polyethylene amines i.e., the polymerized reaction product of ethylene oxide with ethyleneimine, having the general formula :
  • ethoxylated polyethylene amine in particular ethoxylated tetraethylenepentamine, and quaternized ethoxylated hexamethylene diamine.
  • compositions suitable to be used herein may further comprise other additional compounds such as other surfactants, builder system, solvents, perfumes, dyes, suds suppressing agents, enzymes, photobleaching agents, other chelating agents and other minors.
  • additional compounds such as other surfactants, builder system, solvents, perfumes, dyes, suds suppressing agents, enzymes, photobleaching agents, other chelating agents and other minors.
  • the optional ingredients are selected so that they are compatible with said source of active oxygen.
  • Solvents suitable for use herein may be selected from octyl alcohol, isopropyl alcohol, propyl alcohol, and/or furfuryl alcohol.
  • Pyrocatechol is a highly preferred optional ingredient to be used in the liquid compositions according to the present invention.
  • the liquid compositions according to the present invention comprise up to 5% by weight of the total composition of pyrocatechol, preferably from 0.01% to 1% and more preferably from 0.01% to 0.5%.
  • Pyrocatechol improves the chemical stability of the liquid compositions of the present invention that further comprise a source of active oxygen, i.e. lower the decomposition of the bleach and the bleach activator if present. Indeed, it is believed that the chemical stabilising effect of pyrocatechol is twofold. Firstly they may work as radical scavengers and secondly they may interact with the hydrogen peroxide preventing or limiting hydrolysis, therefore reducing the rate of peroxide decomposition.
  • surfactants suitable for use herein are well known in the art and include anionic, nonionic, zwitterionic and cationic surfactants and mixtures thereof.
  • the surfactants suitable for use herein are compatible with hydrogen peroxide and sources thereof.
  • the anionic surfactants which may be used herein include alkali metal salts of alkyl substituted benzene sulphonates, alkali metal alkyl sulphonates, alkali metal alkyl sulphates and alkali metal alkyl ether sulphates derived from for example fatty alcohols and alkyl phenols, alkali metal alkane sulphonates, alkali metal olefm sulphonates and alkali metal sulphosuccinates and alkyl succinates, whereby the sodium salts are preferred, alkyl carboxylates and alkyl ether carboxylates.
  • nonionic surfactants which may be used herein include any liquid or solid ethoxylated C ⁇ -C24 fatty alcohol nonionic surfactant, alkyl ethoxylates/propoxylates and mixtures thereof, fatty acid C6-C24 alkanolamides, C6-C20 polyethylglycol ethers, polyethylene glycol with molecular weight 1000 to 80000 and glucose amides, alkyl pyrrolidones, betaines.
  • Suitable cationic surfactants for use herein include quaternary ammonium compounds of the formula R ⁇ R2R3R N + where R-
  • Zwitterionic surfactants are also suitable optional ingredients for use herein.
  • Suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 24 carbon atoms and another substituent contains, at least, an anionic water-solubilizing group.
  • Particularly preferred zwitterionic materials are the ethoxylated ammonium sulphonates and sulfates disclosed in U.S.
  • compositions herein comprise up to 70% by weight, preferably from 0.1% to 50% by weight of the total composition of a surfactant or mixtures thereof.
  • compositions suitable to be used according to the present invention may further comprise a builder system.
  • Suitable builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R_CH(COOH)CH2(COOH) wherein R is C-JO-20 alkyl or alkenyl, preferably C ⁇
  • Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, 2- tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
  • Suitable builders are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
  • fatty acid builders including saturated or unsaturated C-
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • a preferred builder system for use herein consists of a mixture of citric acid, fatty acids and succinic acid derivatives described herein above.
  • the compositions herein may comprise from 0% to 10%, preferably from 1% to 7% by weight of the total composition of a builder system.
  • compositions are made by combining the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • compositions I II III IV Compositions I II III IV
  • DETPMP diethylene triamine penta methylene phosphonic acid available from Monsanto under the trade name Dequest 2060 or Dequest 4060.
  • MA AA is copolymer of maleic/ acrylic acid, average molecular weight about 70,000.
  • PA is an ethoxylated tetraethylenepentamine, average molecular weight about 70,000.
  • the ca ⁇ et cleaning compositions of examples I to IV exhibit excellent stain removal performance on a variety of stains/soils including particulate stains, greasy/oily stains, bleachable stains like coffee, beverages and enzymatic stains like blood.
  • Composition III is preferably used in manual ca ⁇ et cleaning applications in neat or diluted form.
  • Composition I is preferably used in ca ⁇ et cleaning machines.
  • Compositions II and IV can be used for both applications, they are preferably used diluted when used in ca ⁇ et cleaning machines.
  • laundry pretreater compositions further illustrate the present invention. These compositions are made by combining the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • Propandiol 3 3 3 3 — Acetyl triethy citrate — - - - 3.5 3.5 Water and minors Balance
  • the laundry pretreater compositions V to X provide excellent stain removal performance on a variety of stains including particulate stains, greasy/oily stains, bleachable stains like coffee, beverages and enzymatic stains like blood, when used to pretreat fabrics.

Abstract

The present invention relates to the use of an amine oxide surfactant according to the formula R1R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, or mixtures thereof, in a cleaning composition, to improve the stain removal performance of said composition. The present invention further relates to processes of cleaning carpets and of pretreating fabrics with said compositions.

Description

USE OF AMINE OXIDE SURFACTANTS FOR IMPROVED STAIN REMOVAL PERFORMANCE
Technical Field
The present invention relates to the use of amine oxide surfactants in cleaning compositions and more particularly to their ability to remove stains, soils or combinations thereof from carpets and fabrics.
Background of the Invention
Carpets produced from synthetic or natural fibers and mixtures thereof are commonly used in residential and commercial applications as a floor covering. Various types of fibers can be used in making caφets such as polyamide fibers, polyester fibers as well as wool, cotton or even silk.
However, carpets as well as fabrics, irrespective of whether they are made from natural or synthetic fibers, are all prone to soiling and staining when contacted with many household items. Foods, grease, oils, beverages in particular such as coffee, tea and soft drinks especially those containing acidic dyes can cause unsightly, often dark stains on caφets and fabrics.
Also caφet fibers may become soiled as a result of dirt particles, clay, dust, particulate soils in general, coming into contact with and adhering to the fibers of the caφets. These latter soils often appear in the form of a diffuse layer of soils rather than in the form of spots and tend to accumulate particularly in the so called "high traffic areas" such as near doors as a result of intensive use of the carpets in such areas.
There are a number of caφet cleaning compositions described in the art for removing stains and soils from caφets as well as a number of fabric cleaning compositions described in the art for removing stains and soils from fabrics. However, these compositions do not satisfactorily meet the consumer's needs regarding their cleaning performance on different types of stains and soils. For example, caφet cleaning compositions are not fully satisfactory on removing particulate stains and/or greasy stains, especially in the so called "high traffic areas" of caφets.
Thus the object of the present invention is to provide improved stain removal performance, in a manner which is applicable to a variety of cleaning compositions, i.e. compositions being either in a liquid form, or in a powder form, or in a granular form, and to a variety of applications like caφets and/or fabrics cleaning applications.
It has now been found that the above object can be met by incorporating amine oxide surfactants according to the formula R1R2R3NO, wherein each of R1 , R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, in a cleaning composition. Indeed, it has now been found that said amine oxide surfactants allow to deliver improved stain removal performance on a variety of stains including particulate stains, greasy/oily stains like chocolate, sphagetti sauce, mayonnaise as well as bleachable stains like coffee, tea, and enzymatic stains like blood. The present finding is applicable both in laundry cleaning application, especially in laundry pretreatment, and in carpet cleaning application.
An advantage of the present invention is that it is applicable to all caφet types, especially delicate natural fibers and is also safe to all caφet dye types, particularly sensitive natural dyes used therein. The present invention is particularly suitable for the cleaning of upholstery and car seat coverings.
Another advantage is that the compositions to be used according to the present invention may be applied directly on the caφet without causing damage to the caφet. In addition the cleaning action of the invention commences as soon as the caφet cleaning composition has been applied to the surface. Indeed, the use of the caφθt cleaning compositions of the present invention does not necessarily require rubbing and/or brushing of the carpet.
A further advantage of the present invention is that it is applicable to all types of fabrics, especially delicate fabrics upon pretreatment conditions, e.g., when applied onto the fabrics even for a prolonged period of contact, before said fabrics are washed. Summary of the Invention
The present invention encompasses the use of an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of R1 , R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, in a cleaning composition, to improve the stain removal performance of said composition.
The present invention further encompasses a method of cleaning a carpet wherein a composition comprising an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, is applied to said caφet, wherein said carpet is then optionally rubbed and/or brushed, and wherein said composition rs then removed from said caφet.
The present invention also encompasses a method of pretreating fabrics with a composition comprising an amine oxide surfactant according to the formula R1R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, said method comprising the steps of applying said composition in its neat form onto the fabric, and allowing said composition to remain in contact with said fabric before said fabric is washed.
All amounts, percentages and ratios are given by weight of the total composition in its neat form unless otherwise stated.
Detailed Description of the Invention
In its broadest aspect, the present invention relates to the use of amine oxide surfactants according to the formula R1R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, in a cleaning composition to improve the stain removal performance of said composition.
As an essential ingredient, the compositions to be used according to the present invention comprise an amine oxide surfactant or mixtures thereof. Suitable amine oxide surfactants to be used herein are according to the following formula R1 R2R3NO wherein each of R1 , R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl groups of from 1 to 30 carbon atoms, and preferably of from 1 to 20 carbon atoms. Particularly preferred amine oxide surfactants to be used according to the present invention are amine oxide surfactants having the following formula R1R2R3NO wherein R1 is a saturated linear or branched alkyl group of 1 to 30 alkyl group, preferably of 6 to 18 alkyl group, more preferably of 6 to 14, most preferably of 6 to 10 and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms, and more preferably are methyl groups. In the most preferred embodiment of the present invention said amine oxide surfactants are pure-cut amine oxide surfactants, i.e., a pure single amine oxide surfactant, e.g. Cβ N,N- imethyl amine oxide, as opposed to mixtures of amine oxide surfactants of different chain lenghts.
Suitable amine oxide surfactants for use herein are for instance pure cut C8 amine oxide or pure cut C10 amine oxide or pure cut C14 amine oxide, natural blend C8-C10 amine oxides as well as C12-C16 amine oxides. Said amine oxide surfactants may be commercially available from Hoechst or Stephan.
Indeed, it has now been found that said amine oxide surfactants allow to deliver improved stain removal performance on a variety of stains/soils including particulate stains, greasy/oily stains, bleachable stains and/or enzymatic stains.
Indeed, it has been found that the removal of stains, in particular particulate stains and/or greasy/oily stains and/or bleachable stains and/or enzymatic stains achieved by using a cleaning composition comprising said amine oxide surfactants, is improved, as compared to the removal of stains obtained by using the same composition without said amine oxide surfactants or the same composition but with another surfactant like for instance alkyl sulphate instead of said amine oxide surfactants. By "particulate stains" it is meant herein any soils or stains of particulate nature that can be found on caφets or fabrics, e.g., clay, dirt, dust, mud, concrete and the like.
By "greasy/oily stains" it is meant herein any soils or stains of greasy/oily nature that can be found on caφets or fabrics, e.g., make-up, lipstick, dirty motor oil and mineral oil, greasy food like mayonnaise and spaghetti sauce.
By "bleachable stains" it is meant herein any stains on caφets or fabrics that can be oxidised by bleach, e.g. coffee, tea, wine, grass or fruit juice.
By "enzymatic stains" it is meant herein any soils or stains of enzymatic nature that can be found on carpets or fabrics, e.g., blood.
Also in the preferred embodiment of the present invention wherein the compositions herein further comprise a source of active oxygen, the presence of said amine oxide surfactants improves the chemical stability of said compositions. Indeed, we have observed that improved chemical stability, i.e., lower decomposition of the bleach and the bleach activator, if present, is obtained by adding such an amine oxide surfactant. It is believed that such stability is due to the capacity of the amine-oxide surfactants to limit interactions between the bleach and the bleach activator, if present, possibly through emulsification. It is believed that this stabilising effect is matrix independent.
Furthermore, said amine oxide surfactants, especially pure-cut short chain (C6-C10) amine oxide surfactants have the advantage to reduce the amount of residues left onto fibers being treated with a composition comprising them. Also, the residues left after said composition comprising them has performed its cleaning action are partially in a crystalline form. Indeed, it has been observed that with the compositions according to the present invention comprising said amine oxide surfactants, especially pure-cut amine oxide surfactants, more than 90%, preferably more than 95%, of the residues left onto the fibers are crystals (generally lamellar and/or needle- shaped) with an average particle surface bigger than 300μ2. This results in a process of cleaning caφets whereby the residues left onto the caφets are removed more easily as opposed to residues being sticky and thus difficult to remove by for example vacuum cleaning said caφets. Another advantage of the presence of said amine oxide surfactants, for example mixtures of short chain amine oxide surfactants (C6-C10) with longer chain ones (e.g., C12-C30 amine oxide surfactants), in the compositions according to the present invention, is that they allow to control the foam level and especially the foam persistence in said compositions. This results in compositions being particularly suitable to be used in caφet cleaning machines as well as neat onto caφβts and/or fabrics without formation of high amounts of foam.
Actually, an advantage of the finding of the present invention is that it is applicable in different cleaning processes including caφet cleaning and fabric cleaning especially fabric pretreatment.
Accordingly, such cleaning compositions comprising said amine oxide surfactants are particularly useful as laundry pretreaters, i.e. in a process where said composition is applied in neat form onto soiled portions of fabrics before said fabrics are washed in a separate, typical laundry operation. Preferably, said composition in neat form is left to act on said portions for a period of time before the fabrics are washed in said laundry operation. Preferably, said composition in neat form is not left to dry onto said portions. Preferably, said period of time is in between 1 minute to several hours, more preferably 1 minute to 1 hour, more preferably 1 minute to 30 minutes and most preferably 2 to 10 minutes. Optionally, when said fabrics are soiled with encrustrated stains and soils, said pretreatment process may additionally involve rubbing and scrubbing. It has been observed that in such a pretreatment process, the presence of said amine oxide surfactants improves the stain removal performance on a variety of stains. It is believed that this improvement in stain removal performance is matrix independent.
Such cleaning compositions comprising said amine oxide surfactants are also particularly useful as caφet cleaning compositions. Accordingly, the present invention also encompasses a method of cleaning a caφet wherein a composition comprising an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, is applied to said carpet, wherein said caφet is then optionally rubbed and or brushed, and wherein said composition is then removed from said caφet.
Indeed, in the method of cleaning a carpet according to the present invention the step of applying a composition for the cleaning of caφets as described herein before, may be followed by a rubbing step and/or a brushing step. An advantage of the present invention is that the cleaning action of said compositions commences as soon as said compositions are applied onto said caφet. Thus, the cleaning process of the present invention does not necessarily require rubbing and/or brushing. It is only in the case of highly soiled caφets or in the so called "high traffic areas" that the carpet may be cleaned by applying onto it said composition for the cleaning of carpets according to the present invention, then rubbing and/or brushing it more or less intensively for example by means of a sponge or a brush or other mechanical/electrical device, optionally with the aid of water. In general, the rubbing/brushing-times are between 1 to a few minutes per square meter. After the composition for the cleaning of caφets according to the present invention has been applied onto the caφβt and optionally rubbed and/or brushed, said composition is removed from said caφet, preferably by mechanical means including brushing out and/or vacuum cleaning.
The compositions for the cleaning of caφets according to the present invention may be applied to the caφet to be cleaned either in neat or diluted form, this applies to compositions being either liquid compositions or granular compositions or powder compositions.
By "diluted form" it is meant herein that the compositions for the cleaning of carpets according to the present invention may be diluted by the user, preferably with water. Said compositions can be diluted up to 150 times, preferably up to 50 times and more preferably up to 25 times.
In a preferred embodiment herein, the compositions for the cleaning of caφets according to the present invention are liquid aqueous compositions. Indeed, a liquid aqueous composition, i.e. an aqueous composition for the cleaning of caφets in its neat form or which has been diluted with water by the user or an aqueous composition resulting from the dilution of a granular composition or of a powder composition, is applied to the caφet to be cleaned, said caφet is optionally rubbed and/or brushed, then said composition is left to dry and then removed from said caφet. Indeed, said liquid aqueous composition is left to dry until said composition which combined with dirt has been changed into dry residues. These residues are then removed from the caφet mechanically. Such liquid aqueous compositions may be applied directly onto the area to be treated or applied using a cloth or piece of material such as spraying device or aerosol can, a sponge, a brush or other mechanical/electrical device. In a preferred embodiment of the invention a liquid aqueous composition is applied to the area to be treated by using a spraying device or an aerosol can. Such a spraying device may be trigger operated or pump operated or electrically operated or operated by any source of pressurised gas such as a can or a pressurizer. Such spraying devices are particularly preferable if a large area is to be treated as it facilitates the ease of use for the consumer. The spraying devices ensure uniform coverage of the area to be treated and maximises the advantage of the using liquid aqueous compositions containing peroxides. This is because the application of product by spray best allows the product to be left to dry on the area treated, even without rubbing or brushing. This optimises the action time of the composition and allows the best exploitation of the bleaching action of peroxides.
In another embodiment, the compositions for the cleaning of caφets according to the present invention are granular compositions or powder compositions. Such compositions for the cleaning of caφets according to the present invention may be applied directly onto the area of the caφet to be treated by for example sprinkling said composition over said area or may be applied by using a sponge, a brush, or other mechanical/electrical device preferably in presence of water and then left to dry and then removed from said caφet.
The area to be treated using the compositions according to the present invention may be any size. In addition, a complete section or even a whole caφet may be applied with the composition for the cleaning of caφets according to the present invention. For such puφoses when using a liquid aqueous composition a spraying device with a pump to allow prolonged spraying is particularly useful. The amount of the compositions for the cleaning of caφets according to the present invention applied will depend on the severity of the stains or soils. In the case of stubborn stains more than one application may be required to ensure complete removal of the stain. The caφet cleaning compositions may also be used in order to deodorise the caφet and remove the dinginess of the caφet resulting from a diffused layer of soil which results from general wear.
The compositions for the cleaning of caφets according to the present invention may be used both for manual caφet cleaning and caφθt cleaning machines. For caφet cleaning machines the compositions for the cleaning of caφets according to the present invention, i.e. either liquid compositions or granular compositions or powder compositions, may be preferably diluted according to the machine operating instructions.
The compositions suitable to be used according to the present invention may be formulated either as solids or liquids. In the case where the compositions are formulated as solids for example as granular compositions or powder compositions, they may be applied directly on the surfaces to be treated or they may be diluted with an appropriate solvent, typically water, before use. In liquid form, the compositions are preferably but not necessarily formulated as aqueous compositions. Liquid compositions are preferred herein for convenience of use.
The compositions according to the present invention may further comprise as an optional but highly preferred ingredient a source of active oxygen or mixtures thereof. In the preferred embodiment, said compositions are liquid aqueous compositions and have the advantage, due to the presence of said amine oxide surfactants, to be particularly efficient in terms of overall cleaning performance and to be chemically stable. Indeed, said liquid aqueous compositions according to the present invention do not require pH adjustment prior to use and can be stored for long periods of time prior to use.
A preferred source of active oxygen according to the present invention is hydrogen peroxide or sources thereof. As used herein a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said .compound is in contact with water. Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, metal peroxides and perborates.
In addition other classes of peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof. Suitable classes include dialkylperoxides, diacylperoxides, preformed percarboxylic acids, persilicates, persulphates, organic and inorganic peroxides.
Suitable organic and inorganic peroxides for use in the compositions according to the present invention include diacyl and dialkyl peroxides such as dibenzoyi peroxide, dilauroyl peroxide, dicumyl peroxide, persulphuric acid and mixtures thereof.
Suitable preformed peroxyacids for use in the compositions for the cleaning of caφets according to the present invention include diperoxydodecandioic acid DPDA, magnesium peφhthalatic acid, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
Accordingly, the compositions suitable to be used according to the present invention comprise from 0.1% to 15%, preferably from 0.5% to 10%, more preferably from 1 % to 7% by weight of active oxygen in said compositions.
As used herein, active oxygen concentration refers to the percentage concentration of elemental oxygen, with an oxidation number zero, that being reduced to water would be stoichiometrically equivalent to a given percentage concentration of a given peroxide compound, when the peroxide functionality of the peroxide compound is completely reduced to oxides. The active oxygen sources according to the present invention increase the ability of the compositions to remove colored stains, to destroy malodorous molecules and to kill germs.
The concentration of available oxygen can be determined by methods known in the art, such as the iodimetric method, the permanganometric method and the cerimetric method. Said methods and the criteria for the choice of the appropriate method are described for example in "Hydrogen Peroxide", W. C. Schumb, C. N. Sat.er-f.eld and R. L. Wentworth, Reinhold Publishing Coφoration, New York, 1955 and "Organic Peroxides", Daniel Swern, Editor Wiley Int. Science, 1970. The compositions suitable to be used according to the present invention may further comprise a bleach activator or mixtures thereof, as another optional ingredient. By "bleach activator", it is meant herein a compound which reacts with hydrogen peroxide to form a peracid. The peracid thus formed constitutes the activated bleach. Suitable bleach activators to be used herein include those belonging to the class of esters, amides, imides, or anhydrides. Examples of suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231 and a method for their formation into a prilled form is described in European Published Patent Application EP-A-62 523. Suitable examples of such compounds to be used herein are tetracetyl ethylene diamine (TAED), sodium 3,5,5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n- nonanoyloxybenzenesulphonate (NOBS). Also suitable are N-acyl caprolactam selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam or mixtures thereof. A particular family of bleach activators of interest was disclosed in EP 624 154, and particularly preferred in that family is acetyl triethyl citrate (ATC). Acetyl triethyl citrate has the advantages that it is environmentally friendly as it eventually degrades into citric acid and alcohol. Furthermore, acetyl triethyl citrate has a good hydrolytical stability in the composition upon storage and it is an efficient bleach activator. As used herein and unless otherwise specified, the term bleach activator includes mixtures of bleach activators.
The compositions suitable to be used according to the present invention may comprise up to 30% by weight of the total composition of said bleach activator, or mixtures thereof, preferably from 1% to 20%, and more preferably from 2% to 10%.
The pH of the liquid compositions suitable to be used according to the present invention can be from 0 to 14. In a preferred embodiment, wherein the liquid compositions herein comprise a source of active oxygen, the recommended pH range to achieve good hydrogen peroxide stability is from 0 to 9, preferably between pH 0 and 8, more preferably between pH 0 and 7 and most preferably between 1 and 6. Accordingly, the compositions herein may further comprise an acid to adjust pH. In addition, some acids can have the advantage that they can form small concentrations of the corresponding peracids by reaction with hydrogen peroxide in-situ, thus enhancing the overall performance of the composition. These acids can be further selected so as to have chelating and/or building properties. The acids of the present invention that may be used for these purposes can be organic or inorganic acids, preferably organic acids such as citric, maleic, oxalic succinic, and tartaric acids or inorganic acids such as sulphuric acid.
The composition suitable to be used according to the present invention may comprise various optional ingredients depending on its end use as a laundry cleaning composition or as a caφet cleaning composition.
The compositions suitable to be used according to the present invention may comprise a chelating agent or mixtures thereof, as a highly preferred optional ingredient. Chelating agents suitable to be used herein include chelating agents selected from the group of phosphonate chelating agents, amino carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, and further chelating agents like glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid, or mixtures thereof.
Suitable phosphonate chelating agents to be used herein may include ethydronic acid as well as amino phosphonate compounds, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates. The phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities. Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonates. Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®- Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1 ,2-dihydroxy -3,5-disulfobenzene.
A preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof. Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins. Ethylenediamine N,N'- disuccinic acids are, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA).N- hydroxyethylethylenediamine triacetates, nitrilotri- acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa- acetates, ethanoldiglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms. Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Triton FS® and methyl glycine di-acetic acid (MGDA).
Particularly preferred chelating agents to be used herein are diethylene triamine methylene phosphonate, ethylene N.N'-disuccinic acid, diethylene triamine pantaacetate, glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid or mixtures thereof and highly preferred is salicylic acid. Salicylic acid may be commercially available from Rhone-Poulenc under the name Salicylic Acid®. Indeed, it has been observed that the addition of salicylic acid on top of said amine oxide surfactants results in a synergystic effect on stain removal performance on a variety of stains including particulate stains and/or greasy/oily stains, this especially in the method of cleaning caφets according to the present invention. The compositions suitable to be used according to the present invention comprise up to 5% by weight of the total composition of said chelating agent or mixtures thereof, preferably from 0.1% to 4% and more preferably from 0.1 % to 2%.
The compositions suitable to be used herein may also comprise soil suspending polycarboxylate polymers. Any soil suspending polycarboxylate polymer known to those skilled in the art can be used according to the present invention such as homo- or co-polymeric polycarboxylic acids or their salts including polyacrylates and copolymers of maleic anhydride or/and acrylic acid and the like. Indeed, such soil suspending polycarboxylate polymers can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates to be used herein can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred soil suspending polycarboxylic polymer. Such materials include the water- soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982. Particularly preferred is a copolymer of maleic / acrylic acid with an average molecular weight of about 70,000. Such copolymers are commercially available from BASF under the trade name SOKALAN CP5.
The compositions suitable to be used herein may also comprise soil suspending polyamine polymers as optional ingredients. Any soil suspending polyamine polymer known to those skilled in the art may also be used herein. Particularly suitable polyamine polymers for use herein are polyalkoxylated polyamines. Such materials can conveniently be represented as molecules of the empirical structures with repeating units :
[N R] n Amine form
I
(alkoxy)y
and
R1
I [N+ R] n nX- Quaternized form
I (alkoxy)y
wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R1 may be a C1-C20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most preferably from 10-20; n is an integer of at least 2, preferably from 2-20, most preferably 3-5; and X* is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
The most highly preferred polyamines for use herein are the so-called ethoxylated polyethylene amines, i.e., the polymerized reaction product of ethylene oxide with ethyleneimine, having the general formula :
(EtO) [N CH2 CH2 1 n N (EtO)y
I I
(EtO)y (EtO)y
when y = 2-30. Particularly preferred for use herein is an ethoxylated polyethylene amine, in particular ethoxylated tetraethylenepentamine, and quaternized ethoxylated hexamethylene diamine.
The compositions suitable to be used herein may further comprise other additional compounds such as other surfactants, builder system, solvents, perfumes, dyes, suds suppressing agents, enzymes, photobleaching agents, other chelating agents and other minors. In the preferred embodiment, where the compositions herein comprise a source of active oxygen, the optional ingredients are selected so that they are compatible with said source of active oxygen.
Solvents suitable for use herein may be selected from octyl alcohol, isopropyl alcohol, propyl alcohol, and/or furfuryl alcohol.
Pyrocatechol is a highly preferred optional ingredient to be used in the liquid compositions according to the present invention. The liquid compositions according to the present invention comprise up to 5% by weight of the total composition of pyrocatechol, preferably from 0.01% to 1% and more preferably from 0.01% to 0.5%.
Pyrocatechol improves the chemical stability of the liquid compositions of the present invention that further comprise a source of active oxygen, i.e. lower the decomposition of the bleach and the bleach activator if present. Indeed, it is believed that the chemical stabilising effect of pyrocatechol is twofold. Firstly they may work as radical scavengers and secondly they may interact with the hydrogen peroxide preventing or limiting hydrolysis, therefore reducing the rate of peroxide decomposition.
Other surfactants suitable for use herein are well known in the art and include anionic, nonionic, zwitterionic and cationic surfactants and mixtures thereof. The surfactants suitable for use herein are compatible with hydrogen peroxide and sources thereof.
The anionic surfactants which may be used herein include alkali metal salts of alkyl substituted benzene sulphonates, alkali metal alkyl sulphonates, alkali metal alkyl sulphates and alkali metal alkyl ether sulphates derived from for example fatty alcohols and alkyl phenols, alkali metal alkane sulphonates, alkali metal olefm sulphonates and alkali metal sulphosuccinates and alkyl succinates, whereby the sodium salts are preferred, alkyl carboxylates and alkyl ether carboxylates.
The nonionic surfactants which may be used herein include any liquid or solid ethoxylated Cβ-C24 fatty alcohol nonionic surfactant, alkyl ethoxylates/propoxylates and mixtures thereof, fatty acid C6-C24 alkanolamides, C6-C20 polyethylglycol ethers, polyethylene glycol with molecular weight 1000 to 80000 and glucose amides, alkyl pyrrolidones, betaines.
Suitable cationic surfactants for use herein include quaternary ammonium compounds of the formula RιR2R3R N+ where R-|,R2 and R3 are methyl groups, and R4 is a C12-15 alkyl group, or where R1 is an ethyl or hydroxy ethyl group, R2 and R3 are methyl groups and R4 is a C12-15 alkvl group.
Zwitterionic surfactants are also suitable optional ingredients for use herein. Suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to about 24 carbon atoms and another substituent contains, at least, an anionic water-solubilizing group. Particularly preferred zwitterionic materials are the ethoxylated ammonium sulphonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al., issued December 9, 1975 and 3,929,678, Laughlin et al., issued December 30, 1975. The compositions herein comprise up to 70% by weight, preferably from 0.1% to 50% by weight of the total composition of a surfactant or mixtures thereof.
The compositions suitable to be used according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein. Suitable builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R_CH(COOH)CH2(COOH) wherein R is C-JO-20 alkyl or alkenyl, preferably C<|2-16- or wherein R can be substituted with hydroxyl, sulpho sulphoxyl or sulphone substituents. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, 2- tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
Other suitable builders are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Further suitable builders for use herein are fatty acid builders including saturated or unsaturated C-|0-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid.
A preferred builder system for use herein consists of a mixture of citric acid, fatty acids and succinic acid derivatives described herein above. The compositions herein may comprise from 0% to 10%, preferably from 1% to 7% by weight of the total composition of a builder system.
Examples The following examples will illustrate the present invention. The compositions are made by combining the listed ingredients in the listed proportions (weight % unless otherwise specified).
Compositions I II III IV
(weight %)
Hydrogen peroxide 6 6 7 7
Na CnAS 1 - - - MA/AA 1.0 — — —
DETPMP 0.2 — — —
PA — 1.0 1.0 1.0
C8 Amine Oxide 1 2 2 —
C14 Amine Oxide 1 1 1 —
C10 A mine Oxide 1 — — 3
Water and minors I Sulphuric acid up to pH 5 6 6 6
DETPMP is diethylene triamine penta methylene phosphonic acid available from Monsanto under the trade name Dequest 2060 or Dequest 4060. MA AA is copolymer of maleic/ acrylic acid, average molecular weight about 70,000. PA is an ethoxylated tetraethylenepentamine, average molecular weight about 70,000.
The caφet cleaning compositions of examples I to IV exhibit excellent stain removal performance on a variety of stains/soils including particulate stains, greasy/oily stains, bleachable stains like coffee, beverages and enzymatic stains like blood.
Composition III is preferably used in manual caφet cleaning applications in neat or diluted form. Composition I is preferably used in caφet cleaning machines. Compositions II and IV can be used for both applications, they are preferably used diluted when used in caφet cleaning machines.
The following laundry pretreater compositions further illustrate the present invention. These compositions are made by combining the listed ingredients in the listed proportions (weight % unless otherwise specified).
Compositions V VI VII VIII IX X
(weight %)
Hydrogen peroxide 6 6 6 6 4 4
Anionic surfactants 12 12 12 12 2 4
Dobanol® 45-7 6 12 — 6 6.4 6.4
Dobanol® 23-6.5 6 — 12 6 — —
Dobanol® 23-3 — — — — 8.6 8.6
Amine oxide 1.5 0.5 1.5 3 1 3
Propandiol 3 3 3 3 — — Acetyl triethy citrate — - - - 3.5 3.5 Water and minors Balance
The laundry pretreater compositions V to X provide excellent stain removal performance on a variety of stains including particulate stains, greasy/oily stains, bleachable stains like coffee, beverages and enzymatic stains like blood, when used to pretreat fabrics.
What is claimed is:

Claims

1. The use of an amine oxide surfactant according to the formula R1R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, or mixtures thereof, in a cleaning composition, to improve the stain removal performance of said composition.
2. A method of pretreating fabrics with a composition comprising an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, said method comprising the steps of applying said composition in its neat form onto the fabric, and allowing said composition to remain in contact with said fabric before said fabric is washed.
3. A method of cleaning a caφet to provide improved stain removal performance onto said carpet, wherein a composition comprising an amine oxide surfactant according to the formula R1 R2R3NO, wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl group of from 1 to 30 carbon atoms, is applied to said carpet, wherein said caφet is then optionally rubbed and/or brushed, and wherein said composition is then removed from said caφet.
4. A method according to claim 3 wherein said composition is removed from said carpet by mechanical means including brushing out and/or vacuum cleaning.
5. A method according to claim 4 wherein said composition is a liquid aqueous composition applied neat or diluted to said caφet, or a granular composition or a powder composition which has been diluted typically with water before being applied to said caφet.
6. A method according to claim 5 wherein said neat or diluted composition after having been applied to said caφβt and optionally rubbed and/or brushed, is left to dry before being removed from said caφet.
7. A method according to claims 5 or 6 wherein said composition is used in caφet cleaning machines.
8. A method according claims 5 or 6 wherein said composition is applied to said caφet by means of a spraying device or an aerosol can.
9. A method or use according to any of the preceding claims wherein said composition comprises from 0.1% to 10% by weight of the total composition of said amine oxide surfactant or mixtures thereof, preferably from 0.5% to 6% and more preferably from 0.5% to 3%.
10. A method or use according to any of the preceding claims wherein said amine oxide surfactant is according to the formula R<| R2R3NO wherein R1 is a saturated linear or branched alkyl group of 1 to 30 alkyl group, preferably of 6 to 18 alkyl group, more preferably of 6 to 14, most preferably of 6 to 10, and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched alkyl groups of from 1 to 4 carbon atoms, preferably of from 1 to 3 carbon atoms, and more preferably are methyl groups.
11. A method or use according to any of the preceding claims wherein said composition further comprises a source of active oxygen or mixtures thereof, preferably in the form of hydrogen peroxide or a source thereof and wherein said composition comprises from 0.1% to 15%, preferably from 0.5% to 10% by weight of active oxygen in said composition.
PCT/US1996/003977 1995-03-27 1996-03-25 Use of amine oxide surfactants for improved stain removal performance WO1996030474A1 (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
EP95870026 1995-03-27
EP95870026.2 1995-03-27
US55795P 1995-06-27 1995-06-27
US60/000,557 1995-06-27
EP95203330.6 1995-12-02
EP95203330A EP0735133B1 (en) 1995-03-27 1995-12-02 Activated liquid bleaching compositions
EP96870023.7 1996-03-04
EP96870023A EP0735131A3 (en) 1995-03-27 1996-03-04 Use of amino oxide surfactants for improved stain removal performance

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EP0839900A1 (en) * 1996-10-31 1998-05-06 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
US7503940B2 (en) 2003-02-20 2009-03-17 Harris Research, Inc. Method and system for spot-dyeing textiles
US8957246B2 (en) 2006-10-18 2015-02-17 Ecolab USA, Inc. Method for making a peroxycarboxylic acid
US8999175B2 (en) 2004-01-09 2015-04-07 Ecolab Usa Inc. Methods for washing and processing fruits, vegetables, and other produce with medium chain peroxycarboxylic acid compositions
US9167814B2 (en) 2005-07-06 2015-10-27 Ecolab USA, Inc. Surfactant peroxycarboxylic acid compositions
US9247738B2 (en) 2000-07-12 2016-02-02 Ecolab Usa Inc. Method and composition for inhibition of microbial growth in aqueous food transport and process streams
US9491965B2 (en) 2004-01-09 2016-11-15 Ecolab Usa Inc. Medium chain peroxycarboxylic acid compositions
US9511161B2 (en) 2004-01-09 2016-12-06 Ecolab Usa Inc. Methods for reducing the population of arthropods with medium chain peroxycarboxylic acid compositions
US9560874B2 (en) 1998-08-20 2017-02-07 Ecolab Usa Inc. Treatment of animal carcasses
WO2017215932A1 (en) 2016-06-13 2017-12-21 Unilever N.V. Foamable cleaning composition containing hydrogen peroxide
US11241658B2 (en) 2018-02-14 2022-02-08 Ecolab Usa Inc. Compositions and methods for the reduction of biofilm and spores from membranes

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0839900A1 (en) * 1996-10-31 1998-05-06 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
US9770040B2 (en) 1998-08-20 2017-09-26 Ecolab Usa Inc. Treatment of animal carcasses
US9560875B2 (en) 1998-08-20 2017-02-07 Ecolab Usa Inc. Treatment of animal carcasses
US9560874B2 (en) 1998-08-20 2017-02-07 Ecolab Usa Inc. Treatment of animal carcasses
US10342231B2 (en) 2000-07-12 2019-07-09 Ecolab Usa Inc. Method and composition for inhibition of microbial growth in aqueous food transport and process streams
US9247738B2 (en) 2000-07-12 2016-02-02 Ecolab Usa Inc. Method and composition for inhibition of microbial growth in aqueous food transport and process streams
US7503940B2 (en) 2003-02-20 2009-03-17 Harris Research, Inc. Method and system for spot-dyeing textiles
US9511161B2 (en) 2004-01-09 2016-12-06 Ecolab Usa Inc. Methods for reducing the population of arthropods with medium chain peroxycarboxylic acid compositions
US9491965B2 (en) 2004-01-09 2016-11-15 Ecolab Usa Inc. Medium chain peroxycarboxylic acid compositions
US8999175B2 (en) 2004-01-09 2015-04-07 Ecolab Usa Inc. Methods for washing and processing fruits, vegetables, and other produce with medium chain peroxycarboxylic acid compositions
US9888684B2 (en) 2004-01-09 2018-02-13 Ecolab Usa Inc. Medium chain perosycarboxylic acid compositions
US10568322B2 (en) 2004-01-09 2020-02-25 Ecolab Usa Inc. Medium chain peroxycarboxylic acid compositions
US9167814B2 (en) 2005-07-06 2015-10-27 Ecolab USA, Inc. Surfactant peroxycarboxylic acid compositions
US9288982B2 (en) 2006-10-18 2016-03-22 Ecolab USA, Inc. Method for making a peroxycarboxylic acid
US9708256B2 (en) 2006-10-18 2017-07-18 Ecolab Usa Inc. Method for making a peroxycarboxylic acid
US8957246B2 (en) 2006-10-18 2015-02-17 Ecolab USA, Inc. Method for making a peroxycarboxylic acid
WO2017215932A1 (en) 2016-06-13 2017-12-21 Unilever N.V. Foamable cleaning composition containing hydrogen peroxide
US11241658B2 (en) 2018-02-14 2022-02-08 Ecolab Usa Inc. Compositions and methods for the reduction of biofilm and spores from membranes

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