(19)
(11)EP 2 787 052 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
13.05.2020 Bulletin 2020/20

(21)Application number: 14168793.9

(22)Date of filing:  19.09.2012
(51)Int. Cl.: 
C11D 11/00  (2006.01)

(54)

DEVELOPMENT OF EXTENSIONAL VISCOSITY FOR REDUCED ATOMIZATION FOR DILUTED CONCENTRATE SPRAYER APPLICATIONS

ENTWICKLUNG VON DEHNVISKOSITÄT ZUR REDUZIERTEN ZERSTÄUBUNG FÜR SPRÜHANWENDUNGEN MIT VERDÜNNTEM KONZENTRAT

DÉVELOPPEMENT DE VISCOSITÉ D'EXTENSION POUR ATOMISATION RÉDUITE POUR DES APPLICATIONS DE PULVÉRISATEUR DE CONCENTRÉ DILUÉ


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 21.09.2011 US 201161537390 P

(43)Date of publication of application:
08.10.2014 Bulletin 2014/41

(62)Application number of the earlier application in accordance with Art. 76 EPC:
12834393.6 / 2758482

(73)Proprietor: Ecolab USA Inc.
St. Paul, MN 55102 (US)

(72)Inventors:
  • Hodge, Charles A.
    Cottage Grove, MN 55016 (US)
  • McGuirk, Christopher M.
    Menasha, WI 54952 (US)
  • Levitt, Mark D.
    West St. Paul, MN 55118 (US)
  • Larson, Dale
    Eagan, MN 55122 (US)
  • Kiesel, Elizabeth R.
    St. Paul, MN 55104 (US)
  • Blattner, Amanda R.
    Prior Lake, MN 55372 (US)

(74)Representative: Godemeyer Blum Lenze Patentanwälte Partnerschaft mbB - werkpatent 
An den Gärten 7
51491 Overath
51491 Overath (DE)


(56)References cited: : 
US-A- 5 364 551
US-B2- 7 566 448
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    TECHNICAL FIELD



    [0001] The present invention is related to the method of using a sprayable composition. In particular, the present invention is related to the method of using sprayable aqueous compositions including an anti-mist component for controlling droplet size.

    BACKGROUND



    [0002] Aqueous sprayable compositions can be applied to a hard surface with a transient trigger spray device or an aerosol spray device. These cleaners have great utility because they can be applied by spray to vertical, overhead or inclined surfaces. Spray devices create a spray pattern of the aqueous sprayable compositions that contacts the target hard surfaces. The majority of the sprayable composition comes to reside on the target hard surfaces as large sprayed-on deposits, while a small portion of the sprayable composition may become an airborn aerosol or mist, which consists of small particles comprising the cleaning composition that can remain suspended or dispersed in the atmosphere surrounding the dispersal site for a period of time, such as between 5 seconds to 10 minutes.

    [0003] US 5,364,551 describes spray-on cleaners that can be delivered by pump or pressurized gas aerosol spray head which have been known to cause respiratory distress in the form of a choking mist. The choking mist associated with aerosol use can be reduced or eliminated by formulating surface cleaning compositions that can be dispensed through a spray head resulting in an aerosol or mist droplet having a median particle size greater than 170 µm. Preferred thickeners have been found for use in the non-choking aerosol or mist compositions.

    [0004] US 7,566,448 B2 relates to compositions comprising high molecular weight polymers, particularly polyethylene oxide polymers, wherein the high molecular weight polymer serves as an anti-misting agent to reduce the potential of aerosol generation from a composition when used in a desired environment. The reference further relates to methods of decreasing enzyme exposure from a personal care or cleaning product comprising a high molecular weight polymer.

    [0005] The aqueous sprayable compositions may be supplied as concentrated solutions which may be diluted with water to form use solutions. Such concentrated solutions reduce transportation and storage costs since the dilution water is not transported or stored but instead is added to the solution at a later time. In some embodiments, it is preferable that the concentrate is stable at elevated temperatures and low temperatures, such as those experienced during transportation and storage.

    SUMMARY



    [0006] The invention relates to a method of using a sprayable composition, the method comprising: dispensing an aqueous sprayable composition as droplets having a mean size of greater than 50 microns using a low velocity sprayer, the aqueous sprayable composition comprising at least one surfactant and between 0.002% and 0.006% by weight of an anti-mist component selected from the group consisting of polyethylene oxide, polyacrylamide and combinations thereof, wherein the aqueous sprayable composition further comprises 0.003% to 10% by weight stability components including an antioxidant and a chelant.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0007] 

    FIG. 1 illustrates the percentage of droplets below 11 microns for stock ready to use sprayable solutions and ready to use sprayable solutions modified with polyethylene oxide when applied with a stock trigger sprayer (i.e., non-low viscosity sprayer).

    FIG. 2 illustrates average droplet size for stock ready to use sprayable solutions and ready to use sprayable solutions modified with polyethylene oxide when applied with a stock trigger sprayer.

    FIG. 3 illustrates average droplet size for stock ready to use sprayable solutions and ready to use sprayable solutions modified with polyethylene oxide when applied with a low viscosity trigger sprayer.


    DETAILED DESCRIPTION



    [0008] The present invention relates to a method of using sprayable compositions including an anti-mist component, such as polyethylene oxide, polyacrylamide, , and combinations thereof. In one embodiment, the method of using sprayable compositions may contain a sufficient amount of anti-mist component such that when the concentrate is diluted with water to form a use solution and is dispensed from a transient trigger sprayer, the use solution exhibits an increased median droplet size and reduced mist or aerosol. In one embodiment, the method of using sprayable use solution produces little or no small particle aerosol. In another embodiment, when dispensed with a low velocity sprayer, the method of using sprayable use solution has a mean droplet size greater than 50 microns. It has been found that increasing the droplet size of the dispensed use solution can reduce inhalation and aerosol and misting.

    [0009] The sprayable compositions can be used in any environment where it is desirable to have larger droplet sizes dispensed from a transient trigger sprayer. For example, the sprayable composition can be used in institutional applications, food and beverage applications, heath care applications, vehicle care applications, pest elimination applications, and laundering applications. Such applications include but are not limited to laundry and textile cleaning and destaining, kitchen and bathroom cleaning and destaining, carpet cleaning and destaining, vehicle cleaning and destaining, cleaning in place operations, general purpose cleaning and destaining, surface cleaning and destaining, particularly hard surfaces, glass window cleaning, air freshening or fragrancing, industrial or household cleaners, antimicrobial cleaning. Methods of using the sprayable compositions are also provided.

    [0010] The method of using sprayable composition includes between about 0.002% and about 0.006% by weight of an anti-mist component selected from the group consisting of polyethylene oxide, polyacrylamide and combinations thereof. The anti-mist component may function to reduce atomization and misting of the sprayable solution when dispensed using a sprayer, including aerosol sprayers and transient trigger sprayers. Example transient trigger sprayers include stock transient trigger sprayers (i.e., non-low velocity trigger sprayer) and low-velocity trigger sprayers, both available from Calmar. Suitable commercially available stock transient trigger sprayers include Calmar Mixor HP 1.66 output trigger sprayer. The anti-mist component may also increase the median particle size of the dispensed use solution, which reduces inhalation of the use solution, and particularly reduces inhalation of the sensitizer or irritant.

    [0011] In one example, the method of using sprayable composition includes polyethylene oxide (PEO) and polyacrylamide. PEO is a high molecular weight polymer. A suitable PEO can have a molecular weight between 3,000,000 and 7,000,000. One commercially available PEO is Polyox WSR 301, which has a molecular weight of 4,000,000 and is available from Dow. A suitable concentration range for PEO is between approximately 0.002% and 0.006% by weight of the aqueous sprayable solution.

    [0012] The anti-mist component may alternatively or additionally include a polyacrylamide. A suitable polyacrylamide can have a molecular weight between 8 million and 16 million, and more suitably between 11 million and 13 million. One commercially available polyacrylamide is SuperFloc® N-300 available from Kemira Water Solutions, Inc. A suitable concentration range for polyacrylamide is between approximately 0.002% and 0.006% by weight of the aqueous sprayable solution. The method of using sprayable compositions includes 0.003% to 10% by weight stability components including an antioxidant and a chelant. The effectiveness of an anti-mist component to reduce misting and increase droplet size may degrade over time. A stability component may reduce degradation of the anti-mist component and improve the self-life of the concentrate sprayable composition. Suitable stability components may include antioxidants and chelants. Example antioxidants include, but are not limited to, Irganox® 5057, a liquid aromatic amine antioxidant, Irganox® 1135, a liquid hindered phenolic antioxidant, Tinogard NOA, and Irgafos 168, all available from BASF. Additional example antioxidants include vitamin E acetate. Example chelants include, but are not limited to: sodium gluconate, sodium glucoheptonate, N-hydroxyethylenediaminetriacetic acid (HEDTA), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraproprionic acid, triethylenetetraaminehexaacetic acid (TTHA), and the respective alkali metal, ammonium and substituted ammonium salts thereof, ethylenediaminetetraacetic acid tetrasodium salt (EDTA), nitrilotriacetic acid trisodium salt (NTA), ethanoldiglycine disodium salt (EDG), diethanolglycine sodium-salt (DEG), and 1,3-propylenediaminetetraacetic acid (PDTA), dicarboxymethyl glutamic acid tetrasodium salt (GLDA), methylglycine-N-N-diacetic acid trisodium salt (MGDA), and iminodisuccinate sodium salt (IDS). Suitable commercially available chelant include Dissolvine® GL-47-S, tetrasodium glutamate diacetate, and Dissolvine® GL-38, glutamic acid, N,N-diacetic acid, tetra sodium salt, both available from Akzo Nobel. A suitable concentration range of the stability components includes between approximately 30 parts per million (ppm) and approximately 100,000 ppm of the aqueous sprayable composition or between approximately 0.003% and 10% by weight. A particularly suitable concentration range of the stability components includes between approximately 100 parts per million (ppm) and approximately 70,000 ppm of the concentrate sprayable composition or between approximately 0.01% and 7% by weight.

    [0013] The method of using sprayable compositions may include a combination of stability components, which may further improve the stability of the composition. For example, the method of using sprayable compositions may include a combination of two or more antioxidants and chelants. In one example, the method of using sprayable composition may include an antioxidant and a chelant. In a further example the method of using sprayable composition may include Irganox® 1135 and Dissolvine® GL-47-S. It has been found that when used in combination the effective amounts of Irganox® 1135 and Dissolvine® GL-47-S are half the effective amounts of each when used alone.

    [0014] The concentrate sprayable composition is a non-Newtonian fluid. Newtonian fluids have a short relaxation time and have a direct correlation between shear and elongational viscosity (the elongational viscosity of the fluid equals three times the shear viscosity). Shear viscosity is a measure of a fluid's ability to resist the movement of layers relative to each other. Elongational viscosity, which is also known as extensional viscosity, is measure of a fluid's ability to stretch elastically under elongational stress. Non-Newtonian fluids do not have a direct correlation between shear and elongational viscosity and are able to store elastic energy when under strain, giving exponentially more elongational than shear viscosity and producing an effect of thickening under strain (i.e., shear thickening). These properties of non-Newtonian fluids result in the sprayable composition that has a low viscosity when not under shear but that thickens when under stress from the trigger sprayer forming larger droplets.

    [0015] The concentrate sprayable composition has a relatively low shear viscosity when not under strain. The shear viscosity can be measured with a Brookfield LVDV-II viscometer using spindle R1, at 50 rpm and room temperature. As described further below, in one example, the shear viscosity of the concentrate sprayable composition is comparable to the shear viscosity of water. A suitable shear viscosity for the concentrate sprayable composition is 40 mPa·s (centipoises) or less. A more preferable shear viscosity is 30 mPa·s (centipoises) or less. In one example, the anti-mist components do not increase the shear viscosity of the concentrate sprayable composition when not under strain and the increased shear viscosity is created by other components, such as the surfactant. In comparison to the low shear viscosity concentrate sprayable composition of the current application, adding xanthan gum to a concentrate produces a Newtonian fluid which is too thick to be used as a concentrate. The method of using the sprayable composition of the current application comprises the formation of a low shear viscosity, water thin, mixture even at high concentrations of the anti-mist component, such as those required for concentrate solutions.

    [0016] In another example, the method of using a flowable concentrate sprayable composition contains a sufficient amount of anti-mist component such that the median particle size of the dispensed use solution is sufficiently large enough to reduce misting. A particularly suitable median particle size is 50 microns or greater. A more particularly suitable median particle size is 70 microns or greater, 100 microns or greater, 150 microns or greater, or 200 microns or greater. The suitable median particle size may depend on the composition of the use solution, and thus of the concentrate sprayable composition. For example, a suitable median particle size for a strongly acidic or alkaline use solution may be 100 microns or greater, and more particularly 150 microns or greater, and more particularly 200 microns or greater. A suitable median particle size for a moderately acidic or alkaline use solution may be about 11 microns or greater, preferably about 50 microns or greater, and more preferably 150 microns or greater. A strongly acid use solution may have a pH of 3 or below, a strongly alkaline use solution may have a pH of 11 or greater, and a moderately acidic or alkaline use solution may have a pH between 3 and 11. In one example, the method of using aqueous sprayable composition comprises concentrate acidic sprayable non-Newtonian compositions that generally include at least one acid, at least one surfactant, and at least one anti-mist component, such as polyethylene oxide (PEO) or polyacrylamide (PAA) and at least one stability component including an antioxidant and a chelant. A suitable concentration range of the components of the concentrate sprayable composition includes between approximately 0.1% and 30% by weight surfactant, between approximately 0.1% and 75% by weight of at least one acid, and between approximately 0.01% and 0.3% PEO or PAA. The concentrate sprayable compositions can be diluted with water to form ready to use solutions.

    [0017] The acid can be a strong acid which substantially dissociates in an aqueous solution such as, but not limited to hydrobromic acid, hydroiodic acid, hydrochloric acid, perchloric acid, sulfuric acid,trichloroacetic acid, trifluroacetic acid, nitric acid, dilute sulfonic acid, and methanesulfonic acid. Weak organic or inorganic acids can also be used. Weak acids are acids in which the first dissociation step of a proton from the acid cation moiety does not proceed essentially to completion when the acid is dissolved in water at ambient temperatures at a concentration within the range useful to form the present sprayable composition. Such inorganic acids are also referred to as weak electrolytes. Examples of weak organic and inorganic acids include phosphoric acid, sulfamic acid, acetic acid, hydroxy acetic acid, citric acid, benzoic acid, tartaric acid, maleic acid, malic acid, fumaric acid, lactic acid, succinic acid, gluconic acid, glucaric acid. Mixtures of strong acid with weak acid or mixtures of a weak organic acid and a weak inorganic acid with a strong acid may also be used.

    [0018] The acid can be present in sufficient quantities such that the concentrate sprayable composition has an acidic pH. In one example, the concentrate sprayable composition has a pH of 4.5 or lower. In another example, the concentrate sprayable composition includes between approximately 7% and 75% by weight acid. In a further example, the concentrate sprayable composition includes between approximately 10% and approximately 65% by weight acid. In a still further example, the concentrate sprayable composition includes between approximately 40% and 60% by weight acid. Highly acidic concentrate sprayable compositions, particularly those including between approximately 40% and 60% by weight acid, containing at least one anti-mist component have demonstrated instability when stored at elevated temperatures for extended periods of time. The stability component may improve the shelf-life of the concentrate sprayable compositions. The acid can also include a fatty acid, such as a fatty acid antimicrobial agent or neutralized salt of a fatty acid. Suitable fatty acids include medium chain fatty acids, including C6-C16 alkyl carboxylic acids, such as hexanoic acid, butyric acid, octanoic acid, heptanoic acid, nonanoic acid, decanoic acid, undecanoic acid, and dodecanoic acid. More suitable fatty acids include a C8-C12 alkyl carboxylic acid, still more suitably C9-C10 alkyl carboxylic acid, such as decanoic acid (capric acid). In one example, the sprayable composition includes at least one fatty acid and has a total acid concentration of between 7% and 45% by weight. In a further example, the fatty acid comprises between 1% and 10% by weight with a total acid concentration between 7% and 45% by weight.

    [0019] The method of using sprayable composition includes a surfactant. A variety of surfactants may be used, including anionic, nonionic, cationic, and amphoteric surfactants. Example suitable anionic materials are surfactants containing a large lipophilic moiety and a strong anionic group. Such anionic surfactants contain typically anionic groups selected from the group consisting of sulfonic, sulfuric or phosphoric, phosphonic or carboxylic acid groups which when neutralized will yield sulfonate, sulfate, phosphonate, or carboxylate with a cation thereof preferably being selected from the group consisting of an alkali metal, ammonium, alkanol amine such as sodium, ammonium or triethanol amine. Examples of operative anionic sulfonate or sulfate surfactants include alkylbenzene sulfonates, sodium xylene sulfonates, sodium dodecylbenzene sulfonates, sodium linear tridecylbenzene sulfonates, potassium octyldecylbenzene sulfonates, sodium lauryl sulfate, sodium palmityl sulfate, sodium cocoalkyl sulfate, sodium olefin sulfonate.

    [0020] Nonionic surfactants carry no discrete charge when dissolved in aqueous media. Hydrophilicity of the nonionic is provided by hydrogen bonding with water molecules. Such nonionic surfactants typically comprise molecules containing large segments of a polyoxyethylene group in conjunction with a hydrophobic moiety or a compound comprising a polyoxypropylene and polyoxyethylene segment. Polyoxyethylene surfactants are commonly manufactured through base catalyzed ethoxylation of aliphatic alcohols, alkyl phenols and fatty acids. Polyoxyethylene block copolymers typically comprise molecules having large segments of ethylene oxide coupled with large segments of propylene oxide. These nonionic surfactants are well known for use in this art area. Additional example nonionic surfactants include alkyl polyglycosides.

    [0021] The lipophilic moieties and cationic groups comprising amino or quaternary nitrogen groups can also provide surfactant properties to molecules. As the name implies to cationic surfactants, the hydrophilic moiety of the nitrogen bears a positive charge when dissolved in aqueous media. The soluble surfactant molecule can have its solubility or other surfactant properties enhanced using low molecular weight alkyl groups or hydroxy alkyl groups.

    [0022] The method of using aqueous sprayable composition can contain cleaning compositions comprising a cationic surfactant component that includes a detersive amount of cationic surfactant or a mixture of cationic surfactants. The cationic surfactant can be used to provide sanitizing properties. In one example, cationic surfactants can be used in either acidic or basic compositions.

    [0023] Cationic surfactants that can be used in the cleaning composition include, but are not limited to: amines such as primary, secondary and tertiary monoamines with C18 alkyl or alkenyl chains, ethoxylated alkylamines, alkoxylates of ethylenediamine, imidazoles such as a 1-(2-hydroxyethyl)-2-imidazoline, a 2-alkyl-1-(2-hydroxyethyl)-2-imidazoline and quaternary ammonium compounds and salts, as for example, alkylquaternary ammonium chloride surfactants such as n-alkyl(C12-C18)dimethylbenzyl ammonium chloride, n-tetradecyldimethylbenzylammonium chloride monohydrate, a naphthylene-substituted quaternary ammonium chloride such as dimethyl-1-naphthylmethylammonium chloride.

    [0024] Amphoteric surfactants can also be used. Amphoteric surfactants contain both an acidic and a basic hydrophilic moiety in the structure. These ionic functions may be any of the anionic or cationic groups that have just been described previously in the sections relating to anionic or cationic surfactants. Briefly, anionic groups include carboxylate, sulfate, sulfonate, phosphonatewhile the cationic groups typically comprise compounds having amine nitrogens. Many amphoteric surfactants also contain ether oxides or hydroxyl groups that strengthen their hydrophilic tendency. Preferred amphoteric surfactants of this invention comprise surfactants that have a cationic amino group combined with an anionic carboxylate or sulfonate group. Examples of useful amphoteric surfactants include the sulfobetaines, N-coco-3,3-aminopropionic acid and its sodium salt, n-tallow-3-amino-dipropionate disodium salt, 1,1-bis(carboxymethyl)-2-undecyl-2-imidazolinium hydroxide disodium salt, cocoaminobutyric acid, cocoaminopropionic acid, cocoamidocarboxy glycinate, cocobetaine. Suitable amphoteric surfactants include cocoamidopropylbetaine and cocoamino ethylbetaine.

    [0025] Amine oxides, such as tertiary amine oxides, may also be used as surfactants. Tertiary amine oxide surfactants typically comprise three alkyl groups attached to an amine oxide (N→O). Commonly the alkyl groups comprise two lower (C1-4) alkyl groups combined with one higher C6-24 alkyl groups, or can comprise two higher alkyl groups combined with one lower alkyl group. Further, the lower alkyl groups can comprise alkyl groups substituted with hydrophilic moiety such as hydroxyl, amine groups, carboxylic groups. Suitable amine oxide materials include dimethylcetylamine oxide, dimethyllaurylamine oxide, dimethylmyristylamine oxide, dimethylstearylamine oxide, dimethylcocoamine oxide, dimethyldecylamine oxide, and mixtures thereof. The classification of amine oxide materials may depend on the pH of the solution. On the acid side, amine oxide materials protonate and can simulate cationic surfactant characteristics. At neutral pH, amine oxide materials are non-ionic surfactants and on the alkaline side, they exhibit anionic characteristics.

    [0026] The method of using acidic sprayable compositions may include water. Suitable concentrations of water include between 25% and 90% by weight. More suitable concentrations of water include between 45% and 70% by weight and between 25% and 45% by weight.

    [0027] In another embodiment, the method of using sprayable composition comprises a concentrate quaternary sprayable composition that generally includes water, a quaternary compound, at least one of PEO, PAAand a stability component. The pH of the concentrate quaternary sprayable composition can be between 4 and 12. Suitable quaternary compounds include quaternary ammonium compounds. When the concentrate quaternary sprayable composition includes PEO or PAA, suitable concentrations include between 75% and 95% by weight water, between 5% and 30% by weight quaternary compounds, less than 1% of at least one fragrance or dye, between 0.002% and 0.006% by weight of at least one of PEO or PAA and between 0.003% and 10% by weight of a stability component. In another example, the concentrate quaternary sprayable composition includes between 10% and 20% by weight quaternary compounds. In a further example, the concentrate quaternary sprayable composition consists essentially of between 75% and 95% by weight water, between 5% and 30% by weight quaternary compounds, less than 1% of at least one fragrance or dye, between 0.002% and 0.006% by weight of at least one of PEO or PAA and between 0.003% and 10% by weight of a stability component.

    [0028] In a further embodiment, the method of using sprayable composition comprises a concentrate sprayable air freshener composition. In one example, the concentrate sprayable air freshener composition includes water, at least one nonionic surfactant, at least one anionic surfactant, at least one of PEO and PAA, , at least one fragrance or dye, a stability component and/or optionally may include a microbiocide. Suitable concentrations when the anti-mist component is PEO or PAA include between 50% and 90% by weight water, between 1% and 15% by weight nonionic surfactant, between 1% and 10% by weight anionic surfactant, between 0.002% and 0.006%by weight of at least one of PEO and PAA, between 0.05% and 15% by weight of at least one fragrance or dye, and may include between 0.003% and 10% by weight of at least one stability component. The concentrate sprayable air freshener composition may include between 0% and 0.1% by weight of a microbiocide, and more preferably may include between 0.03% and 0.1% by weight of microbiocide. In a further example, the sprayable compositions consist essentially of the components listed above.

    [0029] In a still further embodiment, the method of using sprayable composition comprises a concentrate sprayable window glass cleaning composition. The method of using sprayable window glass cleaning composition may include water, a solvent, a surfactant, optionally at least one fragrance or dye, at least one of PEO and PAA and at least one stability component. The method of using sprayable window glass cleaning composition can have a pH of between 2 and 4.5. Suitable solvents include ethanol and 1,3-propanediol, both VOC solvents. "VOC" refers to volatile organic compounds, which have been the subject of regulation by different government entities, the most prominent regulations having been established by the California Air Resource Board in its General Consumer Products Regulation. A compound is non-volatile if its vapor pressure is below 13 Pa (0.1 mm Hg) at 20°C.

    [0030] In one embodiment, suitable compositions comprise between 65% and 98% by weight water, between 0.05% and 15% by weight solvent (such as a VOC solvent or a non-VOC solvent), between 0.01% and 10% by weight surfactant, between 0.002% and 0.006% by weight of PEO, PAA or a combination thereof, and between 0.003% and 10% by weight of at least one stability component. Suitable compositions may alternatively comprise between 85% and 95% by weight water, between 0.5% and 10% by weight solvent, between 0.05% and 10% by weight surfactant, between 0.002% and 0.006% by weight of PEO, PAA or a combination thereof, and between 0.003% and 10% by weight of at least one stability component. Fragrances and/or dyes may be present in amount of between 0% and 0.7% by weight of the concentrate composition. The antimist component of the suitable compositions described above may also include between 0.003% and 10% by weight of at least one stability component.

    [0031] In an alternative embodiment, the method of using sprayable window glass cleaning composition has a low concentration of VOCs and/or a relatively high concentration of biobased content. In one example, the method of using sprayable window glass cleaning composition comprises water, at least one solvent or glycerine, at least one surfactant, optionally at least one fragrance or dye, optionally at least one chelant, optionally at least one dispersant, at least one of PEO and PAA, and at least one stability component.

    [0032] Suitable surfactants include alkyl polyglycosides. Suitable alkyl polyglycosides include but are not limited to alkyl polyglucosides and alkyl polypentosides. Alkyl polyglycosides are bio-based non-ionic surfactants which have wetting and detersive properties. Commercially available alkyl polyglycosides may contain a blend of carbon lengths. Suitable alkyl polyglycosides include alkyl polyglycosides containing short chain carbons, such as chain lengths of less than C12. In one example, suitable alkyl polyglycosides include C8-C10 alkyl polyglycosides and alkyl polyglycosides blends primarily containing C8-C10 alkyl polyglycosides. Suitable commercially available alkyl polyglucosides include Glucopon 215 UP available from BASF Corporation. Alkyl polypentosides are commercially available from Wheatoleo. Suitable commercially available polypentosides include Radia®Easysurf 6781, which contains chain lengths of C8-C10 and is available from Wheatoleo.

    [0033] Suitable solvents include propylene glycol and suitable bio-based alternatives 1,3-propanediol. Alternatively, glycerine may be used when a low VOC, high bio-based content cleaner is desired. Glycerine is a poor solvent. However, it has been found that glycerine can help a cloth "glide" across the surface of a window and reduce streaking.

    [0034] The method of using comprises concentrate window glass cleaning composition can optionally include a sheeting agent, such as an ethylene oxide and propylene oxide block copolymer. Suitable sheeting agents include Pluronic N-3, available from BASF Corporation. In some situations, it may be desirable to exclude ethylene oxide and propylene oxide block copolymers from the concentrate window glass cleaning composition.

    [0035] A dispersant may be added to the concentrate sprayable window glass cleaning composition to assist with dispersing water hardness and other non-hardness materials such as but not limited to total dissolved solids such as sodium salts. Suitable dispersants include sodium polycarboxylates, such as sodium polyacrylate, and acrylate/sulfonated co-polymers. In one example, the sodium polycarboxylate or acrylate/sulfonated co-polymer has a molecular weight less than 100,000. In another example, the sodium polycarboxylate or acrylate/sulfonated co-polymer has a molecular weight less than 50,000. In a further example, the sodium polycarboxylate or acrylate/sulfonated co-polymer has a molecular weight between 5,000 and 25,000. Suitable commercially available polymers include Acusol 460N available from Rohm and Haas and Aquatreat AR-546 available from Akzo Nobel. Suitable chelants include amino-carboxylates such as but not limited to salts of ethylenediamine-tetraacetic acid (EDTA) and methyl glycine di-acetic acid (MGDA), and dicarboxymethyl glutamic acid tetrasodium salt (GLDA). The amino-carboxylates may also be in its acid form. Suitable commercially available MGDAs include but are not limited to Trilon® M available from BASF. Biobased amino-carboxylates, such as GLDA, may also be used. Suitable biobased amino-carboxylates may contain at least 40% bio-based content, at least 45% bio-based content, and more preferably, at least 50% bio-based content. For example, suitable commercially available GLDAs include but are not limited to Dissolvine® GL-47-S and Dissolvine® GL-38 both available from Akzo Nobel, which containapproximately 50% bio-based content.

    [0036] Suitable concentrations for the method of using sprayable window glass cleaning compositions having low VOCs include between 20% and 99.9% by weight water, between 0% and 5% by weight of at least one dispersant, between 0.003% and 10% by weight stability components including a chelant, between 0.05% and 30% by weight solvent or glycerine, between 0.05% and 50% by weight surfactant, between 0% and 0.7% by weight of at least one fragrance or dye and between 0.002%and 0.006% by weight of PEO, PAA or a combination thereof. More suitable concentrations include between 65% and 99.9% by weight water, between 0.01% and 5% by weight of at least one dispersant, between 0.05% and 5% by weight chelant, between 0.05% and 8% by weight solvent or glycerine, between 0.5% and 20% by weight surfactant, between 0% and 0.7% by weight of at least one fragrance or dye, between about 0.002% and 0.006% by weight of PEO, PAA or a combination thereof. Even more suitable concentrations include between 85% and 99.9% by weight water, between 0.01% and 5% by weight of at least one dispersant, between 0.05% and 2% by weight chelant, between 0.05% and 2% by weight solvent or glycerine, between 1% and 10% by weight surfactant, between 0% and 0.7% by weight of at least one fragrance or dye, between 0.002% and 0.006% by weight of PEO, PAA or a combination thereof, and between 0.003% and 10% by weight of at least one stability component. The method of using sprayable window cleaner may further optionally include between 0% and 0.05% by weight sheeting agent.

    [0037] A suitable VOC content of the use solution includes less than 3% VOCs by weight of the use solution, less than 1% VOCs by weight of the use solution, or 0% VOCs by weight of the use solution. The low VOC concentrate window glass cleaning composition may also have a relatively high biobased content. In one example, the low VOC concentrate window glass cleaning composition includes at least 49% biobased content. More suitably, the low VOC concentrate window glass cleaning composition includes at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% biobased content.

    [0038] It is recognized that the above components may be replaced partially or in total with a comparable biobased component. Biobased components are components that are composed, in whole or in significant part, of biological products. The amount of biological components or derivatives is referred to as biobased content, which is the amount of biobased carbon in the material or product expressed as a percent of weight (mass) of the total organic carbon in the material or product. Biobased content can be determined using ASTM Method D6866, entitled Standard Test Methods for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectometry Analysis. More specifically, ASTM Method D6866 uses radiocarbon dating to measure the amount of new carbon present in a product as a percentage of the total organic carbon by comparing the ratio of Carbon 12 to Carbon 14. The water content of a product is not included as part of biobased content as it contains no carbon. It is noted that biobased content is distinct from product biodegradability. Product biodegradability measures the ability of microorganisms present in the disposal environment to completely consume the carbon components within a product within a reasonable amount of time and in a specified environment. In one example, the concentrate cleaning composition includes at least 49% biobased content. More suitably, the concentrate composition includes at least 75%, at least 80%, at least 85%, at least 90%, or at least 95% biobased content.

    Additional Functional Materials



    [0039] The method of using sprayable composition may contain other functional materials that provide desired properties and functionalities to the sprayable composition. For the purposes of this application, the term "functional materials" includes a material that when dispersed or dissolved in a use solution/concentrate solution, such as an aqueous solution, provides a beneficial property in a particular use. Examples of functional materials include but are not limited to: aqueous compatible solvents, sequestrants, metal protectors, dyes/odorants, preservatives, and microbiocides.

    Aqueous Compatible Solvents



    [0040] The method of using sprayable composition can contain a compatible solvent. Suitable solvents are soluble in the aqueous sprayable composition of the invention at use proportions. Preferred soluble solvents include lower alkanols, lower alkyl ethers, and lower alkyl glycol ethers. These materials are colorless liquids with mild pleasant odors, are excellent solvents and coupling agents and are typically miscible with aqueous sprayable compositions of the invention. Examples of such useful solvents include methanol, ethanol, propanol, isopropanol and butanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, mixed ethylene-propylene glycol ethers. The glycol ethers include lower alkyl (C1-8 alkyl) ethers including propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, and others. The solvent capacity of the cleaners can be augmented by using monoalkanol amines.

    Sequestrants



    [0041] The method of using sprayable composition can contain an organic or inorganic sequestrant or mixtures of sequestrants. Organic sequestrants such as citric acid, the alkali metal salts of nitrilotriacetic acid (NTA), EDTA, alkali metal gluconates, polyelectrolytes such as a polyacrylic acid, sodium gluconate can be used herein. The method of using sprayable composition can also comprise an effective amount of a water-soluble organic phosphonic acid which has sequestering properties. Preferred phosphonic acids include low molecular weight compounds containing at least two anion-forming groups, at least one of which is a phosphonic acid group. Such useful phosphonic acids include mono-, di-, tri- and tetra-phosphonic acids which can also contain groups capable of forming anions under alkaline conditions such as carboxy, hydroxy and thio. Among these are phosphonic acids having the formulae: R1N[CH2PO3H2]2 or R2C(PO3H2)2 OH, wherein R1 may be-[(lower)alkylene]N[CH2PO3H2]2 or a third--CH2PO3H2 moiety; and wherein R 2 is selected from the group consisting of C1C6 alkyl.

    [0042] The phosphonic acid may also comprise a low molecular weight phosphonopolycarboxylic acid such as one having 2-4 carboxylic acid moieties and 1-3 phosphonic acid groups. Such acids include 1-phosphono-lmethylsuccinc acid, phosphonosuccinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid.

    [0043] Other organic phosphonic acids include 1-hydroxyethylidene-1,1-diphosphonic acid (CH3C(PO3H2)2OH), available from ThermPhos as Dequest® 2010, a 58-62% aqueous solution; amino [tri(methylenephosphonic acid)] (N[CH2PO3H2]3), available from ThermPhos as Dequest® 2000, a 50% aqueous solution; ethylenediamine [tetra(methylene-phosphonic acid)] available from ThermPhos as Dequest® 2041, a 90% solid acid product; and 2-phosphonobutane-1,2,4-tricarboxylic acid available from Lanxess as Bayhibit AM, a 45-50% aqueous solution. It will be appreciated that, the above-mentioned phosphonic acids can also be used in the form of water-soluble acid salts, particularly the alkali metal salts, such as sodium or potassium; the ammonium salts or the alkylol amine salts where the alkylol has 2 to 3 carbon atoms, such as mono-, di-, or tri- ethanolamine salts. If desired, mixtures of the individual phosphonic acids or their acid salts can also be used.

    [0044] The method of using sprayable composition can also comprise a water soluble acrylic polymer which can act to condition the wash solutions under end-use conditions. Such polymers include polyacrylic acid, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed acrylamidemethacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrilemethacrylonitrile copolymers, or mixtures thereof. Water-soluble salts or partial salts of these polymers such as the respective alkali metal (e.g. sodium or potassium) or ammonium salts can also be used. The weight average molecular weight of the polymers is from 500 to 15,000 and is preferably within the range of from 750 to 10,000. Preferred polymers include polyacrylic acid, the partial sodium salt of polyacrylic acid or sodium polyacrylate having weight average molecular weights within the range of 1,000 to 6,000. These polymers are commercially available, and methods for their preparation are well-known in the art.

    [0045] For example, commercially-available water-conditioning polyacrylate solutions useful in the present sprayable solutions include the sodium polyacrylate solution, Colloid® 207 (Colloids, Inc., Newark, N.J.); the polyacrylic acid solution, Aquatreat®AR-602-A (Alco Chemical Corp., Chattanooga, Tenn.); the polyacrylic acid solutions (50-65% solids) and the sodium polyacrylate powders (m.w. 2,100 and 6,000) and solutions (45% solids) available as the Goodrite®°K-700 series from B. F. Goodrich Co.; and the sodium- or partial sodium salts of polyacrylic acid solutions (m.w. 1000-4500) available as the Acrysol® series from Rohm and Haas. The present method of using sprayable compositions can also comprise sequestrants to include materials such as, complex phosphate sequestrants, including sodium tripolyphosphate, sodium hexametaphosphate, as well as mixtures thereof. Phosphates, the sodium condensed phosphate hardness sequestering agent component functions as a water softener, a cleaner, and a detergent builder. Alkali metal (M) linear and cyclic condensed phosphates commonly have a M2O:P2O5 mole ratio of 1:1 to 2:1 and greater. Typical polyphosphates of this kind are the preferred sodium tripolyphosphate, sodium hexametaphosphate, sodium metaphosphate as well as corresponding potassium salts of these phosphates and mixtures thereof. The particle size of the phosphate is not critical, and any finely divided or granular commercially available product can be employed.

    [0046] Sodium tripolyphosphate is another inorganic hardness sequestering agent. Sodium tripolyphosphate acts to sequester calcium and/or magnesium cations, providing water softening properties. It contributes to the removal of soil from hard surfaces and keeps soil in suspension. It has little corrosive action on common surface materials and is low in cost compared to other water conditioners. Sodium tripolyphosphate has relatively low solubility in water (14 wt%) and its concentration must be increased using means other than solubility. Typical examples of such phosphates being alkaline condensed phosphates (i.e., polyphosphates) such as sodium or potassium pyrophosphate, sodium or potassium tripolyphosphate, sodium or potassium hexametaphosphate.

    Metal Protectors



    [0047] The method of using sprayable compositions can contain a material that can protect metal from corrosion. Such metal protectors include for example sodium gluconate and sodium glucoheptonate.

    Dyes/Odorants



    [0048] Various dyes, odorants including perfumes, and other aesthetic enhancing agents may also be included in the method of using compositions. Examples of suitable commercially available dyes include, but are not limited to: Direct Blue 86, available from Mac Dye-Chem Industries, Ahmedabad, India; Fastusol Blue, available from Mobay Chemical Corporation, Pittsburgh, PA; Acid Orange 7, available from American Cyanamid Company, Wayne, NJ; Basic Violet 10 and Sandolan Blue/Acid Blue 182, available from Sandoz, Princeton, NJ; Acid Yellow 23, available from Chemos GmbH, Regenstauf, Germany; Acid Yellow 17, available from Sigma Chemical, St. Louis, MO; Sap Green and Metanil Yellow, available from Keystone Aniline and Chemical, Chicago, IL; Acid Blue 9, available from Emerald Hilton Davis, LLC, Cincinnati, OH; Hisol Fast Red and Fluorescein, available from Capitol Color and Chemical Company, Newark, NJ; and Acid Green 25, Ciba Specialty Chemicals Corporation, Greenboro, NC.

    [0049] Examples of suitable fragrances or perfumes include, but are not limited to: terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, a jasmine such as C1S-jasmine or jasmal, and vanillin.

    Surface Chemistry Modifiers



    [0050] Various surface chemistry modifiers can be included into the method of using sprayable composition. Examples of suitable commercially available surface chemistry modifiers include Laponite® silicates available from Southern Clay Products, Inc. The surface chemistry modifiers may have high surface free energy and high surface area which leads to interactions with many types of organic compounds. In one example, suitable surface chemistry modifiers have a surface free energy of 200 mjoules/meter2 and a surface area of between 750 and 800 m2/gram. A suitable concentration range for surface chemistry modifiers in the use solution is between 10 ppm and 100 ppm.

    Use Solution



    [0051] The method of using sprayable composition comprises that the concentrate sprayable composition can be diluted with water, known as dilution water, to form a use solution. In general, a concentrate refers to a composition that is intended to be diluted with water to provide a use solution; a use solution is dispersed or used without further dilution.

    [0052] The resulting use solution has a relatively low anti-mist component concentration. In one suitable use solution, the concentration of PEO is between 0.002% and 0.006% by weight. In another example, the concentration of PEO is between 0.003% and 0.005%. In a further example, the concentration of PEO is in the concentrated sprayable solution can be 10 to 200 times greater than the PEO concentration of the use solution.

    [0053] In another suitable use solution, the polyacrylamide concentration is between 0.002% and 0.006% by weight. In a particularly suitable use solution, the polyacrylamide concentration is between 0.003% and 0.006% by weight.

    [0054] In a further suitable use solution, the concentration of PEO, PAA or a combination thereof is between 0.002% and 0.006% by weight. In another example, the concentration of PEO, PAA or a combination thereof is between 0.003% and 0.005%. In a further example, the concentration of PEO, PAA or a combination thereof is in the concentrated sprayable solution can be 10 to 200 times greater than the PEO concentration of the use solution.

    [0055] The resulting use solution can also have a relative low stability component concentration. In one suitable use solution, the stability component concentration is between 0.003% and 10% by weight.

    [0056] As discussed above, the method of using sprayable composition may include an acid. The acid may be present in a sufficient amount such that the solution has a pH of 4.5 or lower. In one example, a suitable acid concentration in the use solution is between 0.1% and 10% by weight of the use solution. The amount of acid present in the use solution may depend on whether the acid is a strong acid or a weak acid. Strong acids may have a greater tendency to lose protons such that a lower amount of strong acid is necessary to achieve the same pH compared to a weak acid. In one example, the use solution contains between 0.1% to 1% strong acid. In another example, the use solution contains between 1% and 10% weak acid.

    [0057] The use solution can be dispensed using an aerosol sprayer or transient stock trigger sprayer (i.e., non-low velocity trigger), which results in limited drifting, misting, and/or atomization of the aqueous use solution. Example transient stock trigger sprayers include but are not limited to Calmar Mixor HP 1.66 output trigger sprayer. Reduction in drift, misting, and atomization can be determined from the droplet size of the applied solution, with an increased droplet size indicating reduced misting and atomization. The increased droplet size also reduces inhalation of the use solution. Preferably, the median droplet size is about 10 mircons or greater, about 50 microns or greater, about 70 microns or greater, about 100 microns or greater, about 150 microns or greater and preferably about 200 microns or greater. There are several methods for determining droplet size including, but not limited to, adaptive high speed cameras, laser diffraction, and phase Doppler particle analysis. Commercially available laser diffraction apparatuses include Spraytec available from Malvern and Helos available from Sympatec.

    [0058] The use solution may also be dispensed using a low velocity trigger sprayer, such as those available from Calmar. A typical transient trigger sprayer includes a discharge valve at the nozzle end of the discharge end of a discharge passage. A resilient member, such as a spring, keeps the discharge valve seated in a closed position. When the fluid pressure in the discharge valve is greater than the force of the resilient member, the discharge valve opens and disperses the fluid. A typical discharge valve on a stock trigger sprayer is a throttling valve which allows the user to control the actuation rate of the trigger sprayer. The actuation rate of the discharge valve determines the flow velocity, and a greater velocity results in smaller droplets. A low velocity trigger sprayer can contain a two-stage pressure build-up discharge valve assembly which regulates the operator's pumping stroke velocity and produces a well-defined particle size. In one example, the two-stage pressure build-up discharge valve can include a first valve having a high pressure threshold and a second valve having a lower pressure threshold so that the discharge valve snaps open and closed at the beginning and end of the pumping process. The low velocity trigger sprayers may result in less drifting, misting and atomization of the use solution, and may reduce the amount of small droplets dispensed. The sprayable composition containing an antimist component may work in synergy with the low velocity trigger sprayer to produce a greater increase in droplet size than expect based on the components alone. In one example, a use solution containing the anti-mist component sprayed with a low velocity trigger sprayer resulted in 0% droplets having a droplet size below 11 microns.

    [0059] The use solution is a non-Newtonian liquid. When not under stress, the use solution has a viscosity similar to water. For example, in one embodiment, the use solution has a viscosity less than 40 mPa·s (40 centipoise).

    [0060] As discussed above, the anti-mist component may increase the droplet size of the use solution when dispensed. The anti-mist component may also increase the average flight distance of the use solution when dispensed from a trigger sprayer. Increasing the average flight distance allows a user to be further away from the target hard surface and may decrease the likelihood of inhaling particulates, particularly particulates that rebound off of the hard surface.

    Embodiments



    [0061] The present invention relates to a method of using aqueous sprayable compositions including between 0.002% and 0.006% by weight of an anti-mist component selected from the group consisting of polyethylene oxide, polyacrylamide and combinations thereof. The method of using sprayable composition of the current invention comprises that the concentrate sprayable composition can be diluted with dilution water to form a use solution, which can be applied to a surface to remove soil using a sprayer device.

    [0062] Exemplary ranges for components of the sprayable composition when provided as a concentrate acidic cleaner, a concentrate highly acidic cleaner, a concentrate neutral quaternary cleaner, a concentrate air freshener, and a concentrate glass window cleaner are provide in Tables 1-6, respectively. Tables 1-6 provided exemplary ranges when the anti-mist component is PEO, PAA or combination thereof.
    Table 1- Concentrate Acidic Cleaner Composition
    ComponentExemplary Range (wt%) PEO, PAA, combinations 
    Water 45-75  
    Acid 7-35  
    Solvent 3-15  
    Non-ionic surfactant 1-5  
    Cationic surfactant 0.5-5  
    Fragrance & dye 0.005-0.3  
    Anti-mist component 0.01 - 0.3  
    Stability component 0.003-10  


    [0063] The concentrate acidic cleaner composition of Table 1 can be diluted with water to 5%-15% concentrate to form a use solution. For example, the use solution of the concentrate acidic cleaner of Table 1 can have a concentration of PEO, PAA or a combination thereof between 0.002% and 0.006% by weight. Suitable acid concentrations in the use solution include between 0.1% and 10% by weight of the use solution.
    Table 2 - Concentrate Highly Acidic Cleaner Composition I
    ComponentExemplary Range (wt%) PEO, PAA, combinations 
    Water 25-50  
    Acid 10-75  
    Surfactant 1.3-10  
    Anti-mist component 0.01-0.3  
    Stability component 0.003-10  


    [0064] The concentrate highly acidic cleaner composition of Table 2 can be diluted with water to 5%-15% concentrate to form a use solution. For example, the use solution of the concentrate acidic cleaner of Table 2 can have a concentration of PEO, PAA or a combination thereof between 0.002% and 0.006% by weight. Suitable acid concentrations in the use solution include between 0.1% and 10% by weight of the use solution.
    Table 3 - Concentrate Highly Acidic Cleaner Composition II
    ComponentExemplary Range (wt%) PEO, PAA, combinations 
    Acid, including a fatty acid antimicrobial agent 7-45  
    Nonionic surfactant 0.1-30  
    Anti-mist component 0.01-0.3  
    Stability component 0.003-10  


    [0065] Suitable nonionic surfactants can be branched or unbranched ethoxylated amine according to one of the following formulas:

    or

            R-N-(CH2CH2O)nH



    [0066] R can be a straight or branched alkyl or alkylaryl substituent. R can be a substituent having from 1 to 24 carbon atoms and each n can be from 1 to 20. R can be derived from coconut oil and n can be between 1 to 14, preferably between 6 to 12 and have an HLB from approximately 10 to 14, where HLB represents the empirical expression for the hydrophilic and hydrophobic groups of the surfactant, and the higher the HLB value the more water-soluble the surfactant. In one suitable branched ethoxylated amine the total EO groups (n + n) are preferably between 6 to 12 or 6 to 10. In another suitable ethoxylated anime, R can be capped or terminated with ethylene oxide, propylene oxide, or butylene oxide units. A suitable CAS number for an ethoxylated amine can be 61791-14-8.

    [0067] The nonionic surfactant may be a medium to short chain carbon group having less than 24 carbon atoms that does not include an alcohol. The ethoxylated amine may also be a cocoamine. Ethoxylated cocoamines are commercially available, for example, under tradenames such as Varonic (Evonik Industries) and Toximul (Stepan Company), including Varonic K-210 and Toximul CA 7.5.

    [0068] The concentrate highly acid cleaner composition of Table 3 can be diluted with water to form a use solution having an acid concentration, including a fatty acid antimicrobial agent, between 1% and 10% by weight. In another example, the use solution of the concentration acidic cleaner of Table 3 can have a concentration of PEO, PAA or a combination thereof between 0.002% and 0.006% by weight.
    Table 4 - Concentrate Neutral Quaternary Cleaner Composition
    ComponentExemplary Range (wt%) PEO, PAA, combinations 
    Water 75-95  
    Quaternary compound 5-30  
    Dye 0.002-0.01  
    Anti-mist component 0.01-0.3  
    Stability component 0.003-10  


    [0069] The concentrate neutral quaternary cleaner composition of Table 4 can be diluted with water to 0.1%-0.5% concentrate to form a use solution. In one example, the use solution of the concentrate neutral quaternary cleaner composition of Table 4 can have a concentration of PEO, PAA or a combination thereof between 0.002% and 0.006% by weight. The use solution of the concentrate neutral quaternary cleaner composition can have a pH between 5 and 11.
    Table 5 - Concentrate Air Freshener Composition
    ComponentExemplary Range (wt%) PEO, PAA, combinations 
    Water, zeolite softened 50-90  
    Nonionic surfactant 1-15  
    Microbiocide 0-0.1  
    Anionic surfactant 1-10  
    Fragrance & dye 0.05-15  
    Anti-mist component 0.01-0.3  
    Stability component 0.003-10  


    [0070] The concentrate air freshener composition of Table 5 can be diluted with water to 3%-10% concentrate to form a use solution.
    Table 6 - Concentrate Window Glass Cleaning Composition
    ComponentExemplary Range (wt%) PEO, PAA, combinations
    Water 20-99.9
    Dispersent 0-5
    Sheeting agent 0-0.05
    Chelant 0.003-10
    Solvent or glycerine 0.05-30
    Surfactant 0.01-50
    Fragrance & dye 0-0.7
    Anti-mist component 0.01-0.3
    Stability component 0.003-10


    [0071] The concentrate window glass cleaning composition of Table 6 can be diluted with water to 0.5%-10% concentrate to form a use solution. The use solution can have a pH between 3 and 10.

    [0072] The concentrate compositions disclosed above in Tables 1-6 may be further concentrated to further reduce the amount of water required to be transported and stored. In one example, the concentrate compositions of Tables 1-6 are concentrated 2 to 4 times. For example, PEO and/or PAA may be present in an amount of between 0.02% to 1.2% by weight of the composition. The stability component may present in concentrations up to 20% by weight or up to 40% by weight of the concentrate composition.

    EXAMPLES



    [0073] The present invention is more particularly described in the following examples that are intended as illustrations only, since numerous modifications and variations within the scope of the present invention will be apparent to those of skill in the art. Unless otherwise noted, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples were obtained or are available from the chemical suppliers described below or may be synthesized by conventional techniques.

    Materials Used



    [0074] Acusol™ 460N: a sodium polycarboxylate (25% active) available available from Dow Chemical, Midland, MI
    Ammonium Hydroxide available from HVC Cincinnati, OH
    Dissolvine®GL-38: a glutamic acid, N,N-diacetic acid, tetra sodium salt available from Akzo Nobel
    Dissolvine®GL-47-S: a tetrasodium glutamate diacetate available from Akzo Nobel
    Glucopon® 215 UP: an aqueous solution of alkyl polyglycosides based on a natural fatty alcohol C8-C10 available from BASF Corporation, Florham Park, NJ
    Glucopon® 425N: an alkyl polyglycoside surfactant available from BASF Corporation, Florham Park, NJ
    Irganox® 1135: a liquid hindered phenolic antioxidant available from Ciba Specialty Chemicals
    Irganox® 5057: a liquid aromatic amine antioxidant available from Ciba Specialty Chemicals
    KF 1955: a fragrance available from Klabin Fragrances, Cedar Grove, NJ
    Liquitint® patent blue: a colourant available from Albright & Wilson, Australia
    Oasis® 146: a neutral quaternary cleaner containing at use dilution about 0.036% quaternary ammonium compound and available from Ecolab, St. Paul, MN
    Oasis® 285: an air freshener solution having a neutral pH and available from Ecolab, St. Paul, MN
    Oasis® 299: an acidic liquid cleaner and disinfectant available from Ecolab, St. Paul, MN
    Pluronic® N-3: an ethylene oxide and propylene oxide based block copolymer available from BASF Corporation, Florham Park, NJ
    Polyox™ WSR 301: a non-ionic polyethylene oxide having a molecular weight of 4,000,00 and available from Dow Chemical, Midland, MI
    Tinogard® NOA: an antioxidant available from BASF
    Trilon® M: an aqueous solution of the trisodium salt of methylglycinediacetic acid (Na3MGDA) available from BASF Corporation, Florham Park, NJ
    Zemea®: Propanediol available from DuPont Tate & Lyle BioProducts Window Cleaner A concentrate: formulated according to Table A
    Lemon-Lift®: a ready to use alkaline bleach detergent available from Ecolab, St. Paul, MN
    Table A
    Deionized water 0-99.9%
    Sodium polycarboxylates 0-5%
    EO/PO block co-polymers 0-5%
    Amino carboxylate 0-10%
    Propylene glycol 0.05-30%
    Alkyl polyglycoside 0.05-50%
    Fragrance 0-1%
    Dye 0-1%


    [0075] Highly acidic cleaner A concentrate: formulated according to Table B
    Table B
    Water 25-50%
    Lactic acid, 88% 5-25%
    Glucopon 425 N, 50% 5-15%
    Citric acid, anhydrous 30-60%

    Example 1 - Elongational Viscosity



    [0076] The apparatus used to measure elongational viscosity in Example 1 comprised five 100-mesh screens packed tightly on top of each other at the base of a 50 mL burette containing a measurable amount of liquid. The mesh screens were contained in an adapter and tubing positioned at the base of the burette. The burette was 74 cm long and had a diameter of 1.5 cm. The adapter and tubing had a length of 10.5 cm, and the mesh screens (i.e., the area available for flow through the adapter and tubing) had a diameter of 1.2 cm. The liquid was forced through the tortuous path formed by the many fine orifices. The time taken for 50 mL of a liquid to flow through the apparatus was measured and correlated to a shear viscosity. The longer the time taken to flow through the packed bed of mesh, the more resistance, and hence, the higher the elongational viscosity.

    [0077] Aqueous solutions comprising Polyox WSR 301 or xanthan gum were prepared according to Table 6, and the time required for 50 grams of the aqueous solution to flow through the apparatus was measured.
    Table 6
    SampleComponentShear viscosity mPa·s (cPs)Time (Sec)
    1 Water 9.6 146
    2 0.1% Polyox 22.4 325
    3 0.05% Polyox 14 265
    4 0.01% Polyox 14 180.3
    5 0.005% Polyox 15.8 165
    6 0.1% xanthan gum 56.6 242


    [0078] As shown in Table 6, the Polyox WSR 301 containing samples took longer to flow through the apparatus while having shear viscosities similar to water. In comparison, the shear viscosity of Sample 6, which contained xanthan gum, was larger than that of water. The increased time to flow through the apparatus indicated an increased elongational viscosity.

    [0079] Samples 2-5, which each includes Polyox, has a viscosity similar to that of water and an elongational viscosity greater than water. The increased elongational viscosity may result in increased droplet size and reduced misting. In comparison, the xanthan gum produced a composition having a significantly increased shear viscosity and elongational viscosity. Because xanthan gum results in an increased shear viscosity and elongational viscosity, xanthan gum would result in a concentrate composition that is too thick for use.

    Example 2 - Stability Test



    [0080] Various concentrate aqueous sprayable solutions were tested to determine their temperature stability. The concentrate sprayable solutions were tested at room temperature (20 ° Celsius to 25° Celsius), 49° Celsius (120° Fahrenheit), 4° Celsius. Observations were made after 96 hours, 240 hours, 336 hours, and 4 weeks. The concentrate sprayable solutions were also exposed to freeze thaw cycles, in which the solutions were frozen and then allowed to thaw at room temperature. The solutions were exposed to four total freeze thaw cycles and observations were made after each cycle.

    Sample 7



    [0081] For Sample 7, polyethylene oxide was added to concentrate Oasis 299. The component concentrations of the solutions are presented below in Table 7.
    Table 7
     Sample 7
    Polyox WSR 301 0.018 g
    Propylene glycol 0.1 g
    Oasis 299 99.88 g
    Total 100 g


    [0082] There was no visually noticeable change in the elongational viscosity or other visually observable property for Sample 7 stored at 49° Celcius (120° Fahrenheit), 4° Celsius, and room temperature after 96 hours, 240 hours, 336 hours, and 4 weeks. After three freeze/thaw cycles, Sample 7 contained ghost tails which disappeared after inversion of the solution. Similar ghost tails were observed after the fourth freeze/thaw cycle of Sample 7, and these ghost tails disappeared after two rotations of the solution. The ghost tails may be caused by decreased solubility of one of the components due to a decrease in temperature. The particulates disappeared after mechanical disturbance (such as mixing) or by returning the solution to room temperature.

    Sample 8



    [0083] For Sample 8, polyethylene oxide was added to Window Cleaner A concentrate of Table A. The component concentrations of Sample 8 are presented below in Table 8.
    Table 8
     Sample 8
    Polyox WSR 301 0.054 g
    Propylene glycol 0.1 g
    Window Cleaner A concentrate 99.85 g
    Total 100 g


    [0084] After 96 hours, 240 hours, 336 hours, and four weeks at 49° Celcius (120° Fahrenheit), 4° Celsius and room temperature, no noticeable change in elongational viscosity or other visually observable property was visually observed for Sample 8. No noticeable change was observed after one and two freeze/thaw cycles of Sample 8. After three freeze/thaw cycles of Sample 8, ghost tails were present but disappeared after inversion of the solution. Similar ghost tails were observed after the fourth freeze/thaw cycle of Sample 8, and these ghost tails disappeared after two rotations of the solution.

    Sample 9



    [0085] For Sample 9, polyethylene oxide was added at 0.001-0.05% to a ready to use solution of Lemon-Lift. The polyethylene oxide appeared to be quickly degraded, and Sample 10 did not pass the stability tests.

    Example 3 - Spray Tests


    Comparative Samples A and B



    [0086] Ready to use solutions were formed from concentrate Samples 7 and 8. The ready to use solutions were sprayed with a trigger sprayer available from Calmar and the mist or aerosol produced by each sample was noted. After four weeks of storage at the specified temperature or four freeze/thaw cycles, concentrate Samples 7 and 8 were returned to room temperature and were diluted with water to form ready-to-use solutions (RTU). Calmar Mixor HP 1.66 output trigger sprayer was used to spray each sample onto a hard surface. The Calmar Mixor HP is not a low-velocity sprayer. The spray test results of RTU Samples 7 and 8 were visually compared to Comparative Samples A and B, respectively. RTU Sample 7 was formed by diluting the formulations of Sample 7 with water at an 5-15% dilution ratio. Comparative Sample A was a ready to use solution of Oasis 299 prepared by diluting liquid concentrate Oasis 299 with water at an 5-15% dilution ratio. RTU Sample 8 was formed by diluting Sample 8 with water to form a solution containing 0.5-10% concentrate by weight. Comparative Sample B was a ready to use solution of window cleaner prepared by diluting Window Cleaner A concentrate with water to form a solution containing 0.5-10% Window Cleaner A concentrate by weight. The visual observations are presented in Table 9 below.
    Table 9
    RTU SampleTemperatureObservations
    RTU Sample 7 Four freeze/thaw cycles Visually reduced misting and increased foaming compared to Comparative Sample A
    RTU Sample 7 4°C Visually reduced misting compared to Comparative Sample A
    RTU Sample 7 49°C (120°F) Marked, noticeable increase in misting compared to RTU Sample 8 after four freeze/thaw cycles or stored at 4°C or room temperature; reduced misting compared to Comparative Sample A
    RTU Sample 7 Room temperature Visually reduced misting and increased foaming compared to Comparative Sample A
    RTU Sample 8 Four freeze/thaw cycles Noticeably narrower spray compared to Comparative Sample B; reduced misting around the spray pattern
    RTU Sample 8 4°C Noticeably narrower spray compared to Comparative Sample B; reduced misting around the spray pattern
    RTU Sample 8 49°C (120°F) Increased misting compared to RTU Sample 10 after four freeze/thaw cycles or stored at 4°C or room temperature; Reduced misting Comparative Sample B
    RTU Sample 8 Room temperature Noticeably narrower spray compared to Comparative Sample B; reduced misting around the spray pattern


    [0087] The addition of polyethylene oxide (Polyox WSR 301) reduced misting in Oasis 299 and Window Cleaner A. The reduction was seen in samples stored at 4°C, room temperature and those subjected to freeze/thaw cycles. Samples stored at 49°C (120°F) also showed an improvement.

    Samples 10-37 and Comparative Samples C, D and E



    [0088] Stability components were investigated to lengthen the shelf life of the concentrate solutions. A stability component was added to concentrate Oasis 299 according to Table 10 and the solutions were stored for four weeks at 49°C (120°F). All solutions contained concentrate Oasis 299, 0.042% by weight Polyox WSR 301, and the specified stability component.
    Table 10
    Sampl eIrgano x 5057Isoasco rbic acidAscor bic acidDissolv ine GL-38Propyle ne glycolGlycerin eSodium metabisul fite
    10 7000 ppm 0 0 0 0 0 0
    11 5000 ppm 0 0 0 0 0 0
    12 3000 ppm 0 0 0 0 0 0
    13 1000 ppm 0 0 0 0 0 0
    14 0 10,000 ppm 0 0 0 0 0
    15 0 7000 ppm 0 0 0 0 0
    16 0 4000 ppm 0 0 0 0 0
    17 0 500 ppm 0 0 0 0 0
    18 0 0 10,000 ppm 0 0 0 0
    19 0 0 7000 ppm 0 0 0 0
    20 0 0 4000 ppm 0 0 0 0
    21 0 0 500 ppm 0 0 0 0
    22 0 0 0 50,000 ppm 0 0 0
    23 0 0 0 20,000 ppm 0 0 0
    24 0 0 0 5000 ppm 0 0 0
    25 0 0 0 3000 ppm 0 0 0
    26 0 0 0 0 50,000 ppm 0 0
    27 0 0 0 0 10,000 ppm 0 0
    28 0 0 0 0 5000 ppm 0 0
    29 0 0 0 0 1000 ppm 0 0
    30 0 0 0 0 0 50,000 ppm 0
    31 0 0 0 0 0 10,000 ppm 0
    32 0 0 0 0 0 5000 ppm 0
    33 0 0 0 0 0 1000 ppm 0
    34 0 0 0 0 0 0 10,000 ppm
    35 0 0 0 0 0 0 5000 ppm
    36 0 0 0 0 0 0 1000 ppm
    37 0 0 0 0 0 0 500 ppm


    [0089] After four weeks, the concentrate solutions were removed from the oven and allowed to return to room temperature. The concentrate solutions were then diluted with water to form 5-15% concentrate ready-to-use solutions. The ready-to-use solutions were sprayed with stock trigger sprayers and the mist or aerosol of each was noted. The spray test results of Samples 10-37 were visually compared to that of Comparative Samples C, D and E. Comparative Sample C was concentrate Oasis 299 containing 0.042% by weight Polyox and stored at room temperature for four weeks. Comparative Sample D was concentrate Oasis 299 containing 0.042% by weight Polyox and stored at 49°C (120°F) for four weeks. Comparative Sample E was concentrate Oasis 299 containing 0.042% by weight Polyox and stored in the dark at room temperature for four weeks.

    [0090] Samples 10-13 and Samples 22-25 exhibited reduced misting compared to the Comparative Sample D. This suggests that Irganox 5057 and GL-38 increase the stability of the anti-mist polymer. None of the other Samples significantly reduced misting compared to Comparative Sample D.

    Samples 38-57



    [0091] Polyacrylamide was investigated as an anti-mist component and additives were added to investigate improved shelf-life. Samples 38-57 included concentrate Oasis 299, 0.0736% SuperFloc N-300 by weight and an additive according to Table 11.
    Table 11
    SampleIrganox 5057Isoascorb ic acidAscorbic acidDissolvin e GL-47Propylene glycolGlycerine
    38 5000 ppm 0 0 0 0 0
    39 1000 ppm 0 0 0 0 0
    40 500 ppm 0 0 0 0 0
    41 0 4000 ppm 0 0 0 0
    42 0 1000 ppm 0 0 0 0
    43 0 500 ppm 0 0 0 0
    44 0 0 4000 ppm 0 0 0
    45 0 0 1000 ppm 0 0 0
    46 0 0 500 ppm 0 0 0
    47 0 0 0 20,000 ppm 0 0
    48 0 0 0 5000 ppm 0 0
    49 0 0 0 3000 ppm 0 0
    50 0 0 0 0 50,000 ppm 0
    51 0 0 0 0 10,000 ppm 0
    52 0 0 0 0 5000 ppm 0
    53 0 0 0 0 1000 ppm 0
    54 0 0 0 0 0 50,000 ppm
    55 0 0 0 0 0 10,000 ppm
    56 0 0 0 0 0 5000 ppm
    57 0 0 0 0 0 1000 ppm


    [0092] After four weeks storage at 120°C (°F), the concentrate solutions were removed from the oven and allowed to return to room temperature. The concentrate solutions were then diluted with water to form 5-15% RTU solutions having a SuperFloc N-300 concentration of 0.007% by weight. The RTU solutions of Samples 38-57 were sprayed using a stock sprayer and visual observations regarding the misting and aerosol of each can be noted. These visual results were compared to that for the RTU solutions of Comparative Samples C, D, and E.

    [0093] Samples 38-40 and Samples 47-49 exhibited reduced misting compared to the Comparative Sample D. This suggests that Irganox 5057 and GL-47 increase the stability of the anti-mist polymer. None of the other Samples significantly reduced misting compared to Comparative Sample D.

    Example 4 - Droplet Size


    Samples 58--65



    [0094] The droplet size distributions of cleaners modified with polyethylene oxide were compared to cleaners that were not modified (i.e., did not contain polyethylene oxide). The droplet size distributions were determined using a HELOS apparatus available from Sympatec GmbH, Clausthal-Zellerfeld, Germany. HELOS determines droplet size by laser diffraction. The droplet size distributions were determined for ready-to-use solutions dispensed with stock trigger sprayers and with low velocity sprayers available from Calmar.

    [0095] To analyze particle size using the Sympatec Helos particle size analyzer, the switch on the particle size analyzer was turned to the #2 position. If the switch was originally in the #0 position, the unit was allowed to stabilize for 30 minutes before testing began. If the switch was originally in the #1 position, the stabilization time was not required and the test could be started immediately. The Sympatec Helos particle size analyzer was in communication with a computer which ran software designed to interpret data from the particle size analyzer.

    [0096] The Sympatec Helos particle size analyzer is capable of measuring drop sizes only in certain ranges depending on the lenses used. The desired lens was placed on the particle size analyzer and a reference measurement was performed to calibrate the particle size analyzer.

    [0097] A sprayer with the test medium was primed. The sprayer was then placed so that the orifice of the sprayer was 8 inches from the lens and the center of the spray went through the laser. The conduct the test, the sprayer was actuated three times at 90 strokes per minute using an automatic actuator. The computer software calculated the particles size distributions.

    [0098] Samples 58-65 were ready-used-solutions formed by diluting the respective concentrate base cleaning composition with water to form a solution containing the weight percentages indicated in Table 12. Modified concentrate base cleaning compositions were formed by added a sufficient amount of polyethylene oxide so that when diluted the respective ready-to-use solution contained 0.003% polyethylene oxide by weight.
    Table 12
    SampleConcentrate base cleaning compositionDilution concentration
    58 Oasis 285 3-10%
    59 Oasis 146 0.1-0.5%
    60 Oasis 299 5-15%
    61 Window Cleaner A (W.C.) 0.5-10%
    62 Modified Oasis 285 3-10%
    63 Modified Oasis 146 0.1-0.5%
    64 Modified Oasis 299 5-15%
    65 Modified Window Cleaner A (W.C.) 0.5-10%


    [0099] FIG. 1 illustrates the percentage of droplets below 11 microns for Samples 58-65 when dispensed with a Calmar Mixor HP 1.66cc output sprayer (i.e., a non-low velocity sprayer). As shown in FIG. 1, the addition of 0.003% polyethylene oxide decreases the percentage of droplets below 11 microns in Oasis 285, Oasis 146, Oasis 299, and Window Cleaner A (W.C.). The percentage of particles 11 microns or above are of interest because it is believed that particles of this size are more resistant to inhalation into the throat and lungs. On average, the addition of 0.003% polyethylene oxide significant decreases the percentage of droplets below 11 microns in Oasis 285, Oasis 146, Oasis 299, and Window Cleaner A by 53%.

    [0100] FIG. 2 illustrates the average droplet size for each stock and modified solution when applied with a Calmar Mixor HP 1.66cc output sprayer (i.e., a non-low velocity sprayer). The addition of 0.003% polyethylene oxide increased the average droplet size in Oasis 285, Oasis 146, Oasis 299, and Window Cleaner A (W.C.) by an average of 28%.

    [0101] FIG. 3 illustrates the average droplet size for each stock and modified solution when applied with a low velocity trigger sprayer available from Calmar. The addition of 0.003% polyethylene oxide increased the droplet size on average by 157.8% for all products tested.

    Example 5 - Stability Test


    Samples 66-88 and Comparative Samples F, G and H



    [0102] The purpose of this experiment was to observe the degradation rate of high molecular weight PEO efficacy via a drop in shear viscosity over time using a Brookfield Viscometer. Samples 66-88 were formed by adding the stability additive specified in Table 13 to the concentrate highly acidic cleaner A of Table B above. Additional Polyox WSR 301 was also added so that the resulting formulations contained 0.2% Polyox WSR 301. The concentration of Polyox WSR 301 was chosen so that the resulting formulation had a viscosity relatively greater than water. The high Polyox WSR 301 concentration was only chosen in order to allow observance of the degradation rate and produced an undesirably thick solution.
    Table 13
    SampleIrganox 5057Irganox 1135Dissolvine GL-47Propylene glycolGlycerineVitamin E acetate
    66 2000 ppm 0 0 0 0 0
    67 1000 ppm 0 0 0 0 0
    68 500 ppm 0 0 0 0 0
    69 100 ppm 0 0 0 0 0
    70 0 2000 ppm 0 0 0 0
    71 0 1000 ppm 0 0 0 0
    72 0 500 ppm 0 0 0 0
    73 0 100 ppm 0 0 0 0
    74 0 0 50,000 ppm 0 0 0
    75 0 0 20,000 ppm 0 0 0
    76 0 0 5000 ppm 0 0 0
    77 0 0 1000 ppm 0 0 0
    78 0 0 0 50,000 ppm 0 0
    79 0 0 0 10,000 ppm 0 0
    80 0 0 0 5000 ppm 0 0
    81 0 0 0 1000 ppm 0 0
    82 0 0 0 0 50,000 ppm 0
    83 0 0 0 0 10,000 ppm 0
    84 0 0 0 0 5000 ppm 0
    85 0 0 0 0 1000 ppm 0
    86 0 0 0 0 0 5000 ppm
    87 0 0 0 0 0 500 ppm
    88 0 0 0 0 0 100 ppm


    [0103] The viscosities of the concentrate solutions were measured with a DV-II+ Viscometer available from Brookfield before storage and after storage for 5 days, 10 days, 18 days, 24 days and 32 days at 49°C (120°F) and at room temperature. To measure the viscosity, the samples were allowed to stabilize at room temperature (22 °C (72°F)) and then tested with the Brookfield Viscometer using spindle RV-2 at 2 RPM and 5 minutes settling time between samples. The after storage viscosity to original viscosity ratio was calculated for each sample ((after storage viscosity / original viscosity)100%) and are presented in Table 14.
    Table 14
    SampleDay 5/Day 1Day 10/Day 1Day 18/Day 1Day 24/Day 1Day 32/Day 1
    66 51.15 39.66 33.91 29.60 29.31
    67 56.51 33.80 32.69 27.91 28.32
    68 56.52 45.15 39.80 34.11 33.19
    69 23.28 59.45 40.21 43.30 37.20
    70 67.95 56.09 53.53 64.10 63.62
    71 77.27 78.57 56.17 49.03 49.35
    72 71.91 51.17 51.17 42.56 42.89
    73 60.55 58.82 49.48 43.34 42.99
    74 88.21 72.01 71.65 61.93 62.29
    75 82.31 76.87 54.08 49.32 49.66
    76 67.69 54.42 55.44 49.66 49.32
    77 53.57 47.08 45.45 46.75 46.43
    78 48.22 40.60 42.51 39.81 39.49
    79 53.77 43.15 42.98 41.35 41.70
    80 55.86 45.86 41.64 43.28 42.59
    81 56.83 54.32 37.77 37.41 38.94
    82 36.15 46.94 34.69 40.23 38.85
    83 49.49 48.15 39.73 39.73 40.66
    84 54.73 45.82 44.36 42.91 42.55
    85 51.90 43.10 47.59 41.03 40.69
    86 57.00 52.67 37.33 42.75 42.42
    87 61.22 48.70 45.91 37.65 38.00
    88 55.67 54.61 56.03 45.83 46.19
    Comp. F 94.24 88.14 72.88 74.92 79.32
    Comp. G 51.44 31.12 24.82 19.78 16.91
    Comp. H 79.65 76.49 71.93 64.56 59.65


    [0104] The results were compared to Comparative Samples F, G and H. Comparative Sample F was highly acidic cleaner A containing 0.2% by weight Polyox and stored at room temperature for four weeks. Comparative Sample G was highly acidic cleaner A containing 0.2% by weight Polyox and stored at 49°C (120°F) for four weeks. Comparative Sample H was highly acidic cleaner A containing 0.2% by weight Polyox and stored in the dark at room temperature for four weeks. After storage for 32 days, Samples 70 and 74 and Comparative Samples F and H had a viscosity ratio greater than 50%. A reduction in viscosity (i.e., a low viscosity ratio) may indicate degradation of Polyox.

    Samples 89-94 and Comparative Sample I



    [0105] The polymer degradation rate for compositions including a combination of antioxidants and chelants were also investigated. The concentrate samples included 0.044% by weight Polyox WSR 301 and the additive specified below in the concentrate highly acidic acid cleaner A.
    Table 15
    SampleDissolvine GL-47, wt %Irganox 1135, wt %Tinogard NOA, wt%
    89 5 0 0
    90 0 0.4 0
    91 0 0 0.4
    92 2.5 0.2 0
    93 2.5 0 0.2
    94 0 0.2 0.2
    Comp. I 0 0 0


    [0106] The concentrate samples were formed by mixing the Polyox WSR 301 and the stability additive with the Glucopon of the highly acidic acid cleaner A for 10 minutes. The Polyox, stability additive, Glucopon mixture was then mixed with the remaining ingredients of highly acidic acid cleaner A for 10 minutes. The samples were allowed to settle overnight at room temperature and then were stored at 49°C (120°F). After a storage period, the samples were removed from the oven, returned to room temperature. A use solution with 0.004% by weight Polyox WSR 301 was created by diluting a portion of the sample with water. The use solutions were sprayed with stock trigger sprayers and the spray patterns were qualitatively observed. The spray patterns were graded based on observed misting or aerosol in the air and the percentage of cleaner contacting the surface of the substrate, with the better spray patterns having less observed misting and a higher amount of cleaner making contact with the substrate.

    [0107] After five days of storage at 49°C (120°F), Samples 89-94 had better spray patterns than Comparative Sample I, and Samples 92 and 93 had the best spray pattern. Similarly, after fourteen days of storage at 49°C (120°F), Samples 89-94 had better spray patterns than Comparative Sample I, and Samples 92 and 93 produced the most preferred spray patterns.

    Example 5 - Polyacrylate Test (removed)


    Samples 95-98 (removed)



    [0108] Table 16 (removed)

    Example 6 -Distance Test


    Samples 100-102 and Comparative Sample J



    [0109] Tests were conducted to investigate the effect of Polyox on the average flight distance of a use solution when dispensed with a stock trigger sprayer using Diazo paper by Dietzgen, which turns blue when exposed to ammonia.

    [0110] First, water and Polyox concentrations were formed according to Table 17 below. Ammonium Hydroxide in an amount of 2.5% by weight was also added to each Sample. The solutions were added to stock trigger sprayers.

    [0111] Next, Diazo paper was arranged along a horizontal surface and the stock trigger sprayer was placed at one end of the paper so that when dispensed the horizontal flight distance of the Sample was parallel with the length of the paper. The solution was dispensed by squeezing the trigger sprayer. Because the Samples included ammonia, the paper turned blue when it was contacted by the Sample and the horizontal flight distance of each droplet was visible. The droplet having the further horizontal flight distance was determined and measured. The test was repeated two additional times and the furthest horizontal fight distance of each trial was averaged. The results are presented in Table 17.
    Table 17
    SamplePolyox WSR 301 (ppm)Flight distance (inch)% increase vs. Comp. J
    100 20 78.3 17.39
    101 40 88.3 32.38
    102 60 112.4 68.5
    Comp. J 0 66.7 n/a


    [0112] As shown in Table 17, Polyox increased the flight distance of the Samples compared to Comparative Sample J, which did not include Polyox.


    Claims

    1. A method of using a sprayable composition, the method comprising: dispensing an aqueous sprayable composition as droplets having a mean size of greater than 50 microns using a low velocity sprayer, the aqueous sprayable composition comprising at least one surfactant and between about 0.002% and about 0.006.% by weight of an anti-mist component selected from the group consisting of polyethylene oxide, polyacrylamide and combinations thereof, wherein the aqueous sprayable composition further comprises 0.003% to 10% by weight stability components including an antioxidant and a chelant.
     
    2. The method of claim 1, wherein dispensing the aqueous sprayable composition comprises dispensing the aqueous sprayable composition as droplets, wherein less than 0.01% of the droplets dispensed have a size less than 11 microns.
     
    3. The method of claim 1, wherein the aqueous sprayable composition further comprises at least one acid and the aqueous sprayable composition has a pH of 4.5 or less.
     
    4. The method of claim 3, wherein the acid includes a fatty acid.
     
    5. The method of claim 1, wherein the aqueous sprayable composition further comprises a quaternary ammonium compound.
     
    6. The method of claim 1, wherein the concentrate aqueous composition includes a dispersant.
     
    7. The method of claim 1, wherein the surfactant includes at least one nonionic surfactant and at least one anionic surfactant.
     


    Ansprüche

    1. Verfahren für eine Verwendung einer sprühbaren Zusammensetzung, wobei das Verfahren Folgendes umfasst: Verteilen einer wässrigen sprühbaren Zusammensetzung als Tröpfchen mit einer durchschnittlichen Größe von über 50 Mikrometern unter Verwendung eines Sprühgeräts mit niedriger Geschwindigkeit, wobei die wässrige sprühbare Zusammensetzung, die wenigstens ein Tensid und zwischen etwa 0,002 und etwa 0,006 Gew.-% einer Antinebelkomponente umfasst, ausgewählt ist aus der Gruppe, die aus Polyethylenoxid, Polyacrylamid und Kombinationen davon besteht, wobei die wässrige sprühbare Zusammensetzung ferner 0,003 bis 10 Gew.-% Stabilitätskomponenten einschließlich eines Antioxidationsmittels und eines Chelatbildners umfasst.
     
    2. Verfahren nach Anspruch 1, wobei die wässrige sprühbare Zusammensetzung ein Verteilen der wässrigen sprühbaren Zusammensetzung als Tröpfchen umfasst, wobei weniger als 0,01 % der Tröpfchen, die verteilt werden, eine Größe von weniger als 11 Mikrometer aufweisen.
     
    3. Verfahren nach Anspruch 1, wobei die wässrige sprühbare Zusammensetzung ferner wenigstens eine Säure umfasst und die wässrige sprühbare Zusammensetzung einen pH-Wert von höchstens 4,5 aufweist,
     
    4. Verfahren nach Anspruch 3, wobei die Säure eine Fettsäure beinhaltet.
     
    5. Verfahren nach Anspruch 1, wobei die wässrige sprühbare Zusammensetzung ferner eine quaternäre Ammoniumverbindung umfasst.
     
    6. Verfahren nach Anspruch 1, wobei die konzentrierte wässrige Zusammensetzung ein Dispergiermittel beinhaltet.
     
    7. Verfahren nach Anspruch 1, wobei das Tensid wenigstens ein nichtionisches Tensid und wenigstens ein anionisches Tensid beinhaltet.
     


    Revendications

    1. Procédé d'utilisation d'une composition pulvérisable, le procédé comprenant : la distribution d'une composition aqueuse pulvérisable sous forme de gouttelettes ayant une taille moyenne supérieure à 50 microns à l'aide d'un pulvérisateur à faible vitesse, la composition aqueuse pulvérisable comprenant au moins un tensioactif et entre environ 0,002 % et environ 0,006 % en poids d'un composant anti-buée choisi dans le groupe constitué d'oxyde de polyéthylène, de polyacrylamide et de leurs combinaisons, la composition aqueuse pulvérisable comprenant en outre de 0,003 % à 10 % en poids de composants de stabilité comportant un antioxydant et un chélateur.
     
    2. Procédé selon la revendication 1, dans lequel la distribution de la composition aqueuse pulvérisable comprend la distribution de la composition aqueuse pulvérisable sous forme de gouttelettes, moins de 0,01 % des gouttelettes distribuées ayant une taille inférieure à 11 microns.
     
    3. Procédé selon la revendication 1, dans lequel la composition aqueuse pulvérisable comprend en outre au moins un acide et la composition aqueuse pulvérisable a un pH de 4,5 ou moins.
     
    4. Procédé selon la revendication 3, dans lequel l'acide comporte un acide gras.
     
    5. Procédé selon la revendication 1, dans lequel la composition aqueuse pulvérisable comprend en outre un composé d'ammonium quaternaire.
     
    6. Procédé selon la revendication 1, dans lequel la composition aqueuse concentrée comporte un dispersant.
     
    7. Procédé selon la revendication 1, dans lequel le tensioactif comporte au moins un tensioactif non ionique et au moins un tensioactif anionique.
     




    Drawing












    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description