![]() Neutral floor cleaner
专利摘要:
Compositions and methods for improved cleaning using neutral cleaners are disclosed. In particular, neutral pH cleaning compositions according to the invention employ a synergistic combination of water insoluble surfactants and an anionic hydrotropes capable of forming a stable, low-foaming solution. The neutral cleaning solutions provide significant benefits over water insoluble microemulsions traditionally used for neutral cleaning compositions and provide at least equivalent cleaning efficacy as non-neutral cleaning compositions. 公开号:AU2013221822A1 申请号:U2013221822 申请日:2013-02-12 公开日:2014-07-03 发明作者:Traci Gioino;Catherine Hanson;Yvonne Marie Killeen;Kim R. Smith;Andrew Wold 申请人:Ecolab USA Inc; IPC主号:C11D1-68
专利说明:
WO 2013/122934 PCT/US2013/025744 TITLE: NEUTRAL FLOOR CLEANER FIELD OF THE INVENTION The invention relates to compositions, kits and methods for improved 5 cleaning using neutral cleaners. In particular, neutral pH floor cleaners are disclosed using a synergistic combination of water insoluble surfactants with an anionic hydrotrope forming a stable, low-foaming solution. BACKGROUND OF THE INVENTION 10 A variety of compositions are available for cleaning and/or treating hard surfaces, including architectural surfaces such as floors to reduce soil contamination. Neutral cleaning treatments continue to gain popularity among consumers wanting an environmentally responsible hard surface solution that reduces environmental impact. In addition, such neutral hard care surface solutions must provide clean, 15 bright and shiny surfaces without increasing operational costs. It would be beneficial to provide a surface treatment composition that provides enhanced cleaning performance over current neutral cleaners, as well as meets the requirements for Green Seal compliance reflecting the low toxicity of the composition as well as eliminates the need for use of personal protective equipment 20 by an end-user. Accordingly, it is an objective of the claimed invention to develop neutral cleaning solutions (i.e. approximately neutral pH) while minimizing raw material costs. A further object of the invention is to improve upon commercially-available 25 water insoluble microemulsions for cleaning hard surfaces. A further object of the invention is a neutral cleaning composition that provides at least equivalent cleaning efficacy as non-neutral (i.e. alkaline) cleaning compositions. A still further object of the invention is to provide a neutral cleaning 30 composition having a low-foaming profile. 1 WO 2013/122934 PCT/US2013/025744 BRIEF SUMMARY OF THE INVENTION In an embodiment of the invention, a concentrated neutral floor treatment composition includes from about 1-50 wt-% of at least two water-insoluble surfactants, wherein a first surfactant is a branched alcohol alkoxylate and a second 5 surfactant is an ethylene oxide/propylene oxide copolymer; and about 1-50 wt-% of a water-soluble anionic hydrotrope; and about 20-90 wt-% water, wherein the composition has a neutral pH and forms a clear solution. In another embodiment of the invention, a concentrated neutral floor treatment composition includes about 1-10 wt-% of a water-insoluble Guerbet 10 ethoxylate having the formula CH 3 (CH 2 )nCHCH 2 O(CH 2 CHO)mH I I R IR 2 15 about 1-50 wt-% of a water-insoluble EO-PO copolymer; about 1-50 wt-% of a water-soluble anionic hydrotrope; and about 20-90 wt-% water, wherein the composition has a neutral pH and forms a clear solution. Further embodiments of the invention include a kit comprising a liquid 20 detergent composition, wherein said composition is the neutral cleaning composition; a container; and instructions for use. Kits according to the invention may also include a removal agent for use in applying the neutral cleaning compositions and removing a plurality of soils. Additional embodiments provide for methods of cleaning a hard surface 25 comprising: applying to the hard surface a neutral cleaning composition comprising about 1-10 wt-% a water-insoluble Guerbet ethoxylate, about 1-50 wt-% of a water insoluble EO-PO copolymer surfactant, about 1-50 wt-% of a water-soluble anionic hydrotrope and about 20-90 wt-% of water, wherein the composition has a neutral pH and forms a clear solution. Methods according to the invention may also include 30 a first step of diluting the composition into a use solution with water before applying the composition to a hard surface, and wherein the dilution provides a dispensing rate of a use solution of the neutral cleaning composition from about 0.1 oz./gal to about 10 oz./gal. 2 WO 2013/122934 PCT/US2013/025744 The methods and compositions of the invention provide at least equivalent cleaning efficacy in comparison to alkaline solutions and/or microemulsions of the water-insoluble surfactants of the invention. The equivalent cleaning efficacy to alkaline cleaning compositions provides significant benefits in the way of user 5 safety and safety for application of the compositions to all substrates. Additional benefits of the invention include composition formulations eliminating the need for use of personal protective equipment by an end-user as a result of compliance with regulatory standards (e.g. Global Harmonized System of Classification and Labeling of Chemicals (GHS)). 10 While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive. 15 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a comparison of cleaning efficacy of neutral cleaning compositions in comparison to commercially-available controls (positive (Expl-13) and negative controls (ExpI-10, Exp1-1 1, Expl- 12)). 20 FIG. 2 shows a comparison of cleaning efficacy of neutral cleaning compositions according to the invention (Exp3-15, Exp3-16, Exp3-17) in comparison to commercially-available controls (positive (Exp3-19) and negative controls (Exp3-18). FIG. 3 shows a comparison of cleaning efficacy of neutral cleaning 25 compositions according to the invention (Exp4-20, Exp4-21, Exp4-22) in comparison to commercially-available controls (positive (Exp4-25) and negative controls (Exp4-24)). Various embodiments of the present invention will be described in detail with reference to the drawings, wherein like reference numerals represent like parts 30 throughout the several views. Reference to various embodiments does not limit the scope of the invention. Figures represented herein are not limitations to the various 3 WO 2013/122934 PCT/US2013/025744 embodiments according to the invention and are presented for exemplary illustration of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 5 The present invention relates to neutral cleaning compositions for dispensing at varying rates from about 0.1 oz./gal to about 10 oz./gal. The neutral cleaning compositions provide improved cleaning performance in comparison to commercially-available neutral cleaners. The neutral cleaning compositions, kits and methods according to the invention have many advantages over conventional 10 neutral cleaning compositions. For example, the cleaning compositions form stable solutions, have low foaming profiles, beneficially low toxicity levels (e.g. Green Seal compliant) and provide at least equivalent cleaning efficacy in comparison to non-neutral compositions. The embodiments of this invention are not limited to particular neutral 15 cleaning compositions, kits and methods of use thereof, which can vary and are understood by skilled artisans. It is further to be understood that all terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting in any manner or scope. For example, as used in this specification and the appended claims, the singular forms "a," "an" and "the" can 20 include plural referents unless the content clearly indicates otherwise. Further, all units, prefixes, and symbols may be denoted in its SI accepted form. Numeric ranges recited within the specification are inclusive of the numbers defining the range and include each integer within the defined range. So that the present invention may be more readily understood, certain terms 25 are first defined. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention pertain. Many methods and materials similar, modified, or equivalent to those described herein can be used in the practice of the embodiments of the present invention without undue experimentation, the 30 preferred materials and methods are described herein. In describing and claiming the embodiments of the present invention, the following terminology will be used in accordance with the definitions set out below. 4 WO 2013/122934 PCT/US2013/025744 The term "about," as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, 5 source, or purity of the ingredients used to make the compositions or carry out the methods; and the like. The term "about" also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about", the claims include equivalents to the quantities. 10 The term "cleaning" means to perform or aid in soil removal, bleaching, microbial population reduction, rinsing, or combination thereof. The term "hydrotrope" means a material used in a composition to maintain a single phase neat or aqueous composition or solubilisate (liquid solution). Such hydrotrope may also be used in aspects of embodiments and/or embodiments of the 15 present invention. Hydrotropy is a property that relates to the ability of a material to improve the solubility or miscibility of a substance in liquid phases in which the substance tends to be insoluble. Without being limited to a particular theory of the invention, a hydrotrope modifies a formulation to increase the solubility of an insoluble substance or creates micellar or mixed micellar structures resulting in a 20 stable suspension of the insoluble substance. The term "weight percent," "wt-%," "percent by weight," "% by weight," and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, "percent," "%," and the like 25 are intended to be synonymous with "weight percent," "wt-%," etc. The compositions, kits and methods of the present invention may comprise, consist essentially of, or consist of the components/ingredients of the present invention as well as other components/ingredients described herein. As used herein, "consisting essentially of" means that the methods, systems, apparatuses and 30 compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and 5 WO 2013/122934 PCT/US2013/025744 novel characteristics of the claimed methods, systems, apparatuses, and compositions. While an understanding of the mechanism is not necessary to practice the present invention and while the present invention is not limited to any particular 5 mechanism of action, it is contemplated that, in some embodiments, the synergistic surfactant combination of a water-insoluble Guerbet ethoxylate, a water-insoluble EO-PO copolymer, and an anionic hydrotrope provides improved neutral cleaning solutions. Without being limited to a particular mechanism of action of the synergistic combination according to the invention, in one aspect it is hypothesized 10 that the combination of water-insoluble surfactants and anionic hydrotrope interacts to form a pseudo-ring structure that captures oily/greasy soils, providing enhanced cleaning efficacy over commercially-available neutral cleaning compositions. According to a particular theory, the double tails of the Guerbet ethoxylate may associate with the PO groups in the EO-PO copolymers, whereas the EO groups 15 avoid this hydrophobic area and point out into the water solution. Compositions According to an embodiment of the invention the neutral cleaning compositions comprise, consist of and/or consist essentially of a combination of water-insoluble surfactants and an anionic hydrotrope having an approximately 20 neutral pH. The compositions may optionally include additional functional ingredients. The compositions unexpectedly provide clear, water-soluble products providing significant utility for use as hard surface cleaners. The clear solutions are suitable for use as a dilutable detergent concentrate or as a ready-to-use product. According to the invention, a concentrate refers to a composition that is intended to 25 be further diluted with water to provide a use composition. A use composition refers to a composition that can be applied to surfaces to provide detersive activity. In general, a use composition can have a solids content of less than about 90 wt-%, whereas the solids content refers to the weight percent of non-water components. In an aspect of the invention the pH of the neutral cleaning composition is 30 between about 6-9, preferably between about 6-8.5, more preferably between about 7-8. In a further aspect, the pH of the neutral cleaning composition is about 7. 6 WO 2013/122934 PCT/US2013/025744 The neutral cleaning compositions of water-insoluble surfactants and an anionic hydrotrope are dissolved in water to form a stable, clear solution. In general, a clear solution is a composition having a clarity similar to a composition containing only water. The compositions are distinct from detersive compositions in 5 the prior art where combinations of water-insoluble surfactants, such as Guerbet ethoxylates (e.g. Lutensol XP-50, BASF) and/or EO-PO copolymer (Pluronic N3), form water insoluble microemulsions. These are distinct from the water soluble solutions formed by the neutral cleaning compositions of the invention. Unexpectedly, the neutral cleaning compositions uses a combination of these water 10 insoluble surfactants (e.g. Lutensol XP-50 and Pluronic N3) to provide a stable solution as opposed to a microemulsion. It is further unexpected to obtain the synergistic activity of the water-insoluble surfactants, which would be expected to have superior cleaning efficacy in an alkaline microemulsion of the prior art as opposed to the stable, neutral solutions of the present invention. This invention 15 overcomes the significant difficulties associated with microemulsions, such as the narrow range of thermal phase stability. Beneficially the compositions of the invention avoid the difficulty of phase separation during storage, as a result of converting the water-insoluble surfactants into a true solution. Still further, the compositions are low-foaming, preferably non-foaming. 20 The compositions according to the invention may be provided in various forms for providing the detersive solution. In an aspect of the invention, the compositions are provided as a liquid. In additional aspects of the invention, the compositions are provided as a solid, gel, foam, powders, agglomerates and/or aerosol spray. In a preferred embodiment, the neutral cleaning composition is not a 25 solid, gel, foam, or aerosol spray. The compositions may be dispensed from single or multi-use packaging in the various physical forms. Surfactants The neutral cleaning compositions of the invention include a combination of water-insoluble surfactants. A variety of surfactants can be used to provide 30 synergistic detersive properties, including, but not limited to nonionic surfactants. Exemplary nonionic surfactants that can be used are commercially available from a number of sources. A discussion of surfactants is provided in Kirk-Othmer, 7 WO 2013/122934 PCT/US2013/025744 Encyclopedia of Chemical Technology, Third Edition, volume 8, pages 900-912, incorporated herein by reference. In an aspect of the invention, the compositions include a synergistic combination of water-insoluble surfactants. In an further aspect, the compositions 5 include synergistic combination of nonionic, water-insoluble surfactants. In an aspect of the invention, the synergistic combination of water-insoluble surfactants includes a branched alcohol alkoxylate (e.g. Guerbet ethoxylate) and an EO-PO copolymer. In a further aspect, the water-insoluble EO-PO copolymer may be a traditional EO-PO copolymer, a reverse EO-PO copolymer, and/or combinations of 10 the same. Branched Alcohol Alkoxylates Particularly suitable water-insoluble surfactants include branched alcohol alkoxylates. Further description of these surfactants is found in U.S. Patent 7,530,361 titled "Detergent Composition Containing Branched Alcohol Alkoxylate 15 and Compatibilizing Surfactant, and Method for Using," which is herein incorporated by reference in its entirety. Preferred branched alcohol alkoxylates include Guerbet ethoxylates. Guerbet ethoxylates suitable for use according to the invention have the following formula: 20 CH 3 (CH 2 )nCHCH 2 O(CH 2 CHO)mH I I R IR 2 In an aspect of the invention the Guerbet ethoxylate is further defined wherein RI is 25 C2-C20 alkyl and R2 is H or C1-C4 alkyl. In a further aspect of the invention, the Guerbet ethoxylate is defined wherein "n" is an integer between 2 and 20 and wherein "m" is an integer between 1 and 40. In a preferred aspect of the invention, the branched alcohol alkoxylate is a Guerbet ethoxylate that is prepared from a Guerbet alcohol by dimerization of 30 alkenes (e.g. butane). The branched alcohol alkoxylates, including Guerbet ethoxylates, can be prepared according to U.S. Pat. Nos. 6,906,320, 6,737,553 and 5,977,048, the disclosure of these patents are herein incorporated by reference in their entirety. 8 WO 2013/122934 PCT/US2013/025744 Exemplary branched alcohol alkoxylates include those available under the tradenames Lutensol XP-30 and Lutensol XP-50 (BASF Corporation). In general, Lutensol XP-30 can be considered to have 3 repeating ethoxy groups, and Lutensol XP-50 can be considered to have 5 repeating ethoxy groups. 5 Branched alcohol alkoxylates can be classified as relatively water insoluble or relatively water soluble. In general, a water insoluble branched alcohol alkoxylate can be considered an alkoxylate that, when provided as a composition containing 5 wt-% of the branched alcohol alkoxylate and 95 wt-% water, has a tendency to deposit on a surface and form a greasy film. Lutensol XP-30 and Lutensol XP-50 10 from BASF Corporation are examples of water-insoluble branched alcohol alkoxylates. According to an embodiment of the invention a branched alcohol alkoxylate, preferably a water-insoluble Guerbet ethoxylate has from about 10 wt-% to about 90 wt-% ethylene oxide, from about 20 wt-% to about 70 wt-% ethylene oxide 15 preferably from about 30 wt-% to about 60 wt-% ethylene oxide. According to an embodiment of the invention, the branched alcohol alkoxylate, preferably a water-insoluble Guerbet ethoxylate, is present in a concentrate compositions (and thereafter a use solution) in amounts compliant with regulatory standards (e.g. GHS) for eliminating the need for use of personal 20 protective equipment by an end-user. Beneficially, neutral cleaning compositions according to the invention having less than a regulatory threshold amount of the water-insoluble Guerbet ethoxylate do not require the use of personal protective equipment by an end-user.. In a further aspect of the invention, the amount of branched alcohol alkoxylate is compliant with the 25 GS37 standards for environmentally-friendly and safe hard surface cleaners. In a still further aspect of the invention, the amount of branched alcohol alkoxylate meets GHS standards for elimination of required use of personal protective equipment by an end-user. Ethylene Oxide - Propylene Oxide Copolymers 30 Particularly suitable water-insoluble surfactants include nonionic surfactants. Exemplary surfactants include, but are not limited to, those having a polyalkylene oxide polymer as a portion of the surfactant molecule. Such nonionic surfactants 9 WO 2013/122934 PCT/US2013/025744 include, but are not limited to: chlorine-, benzyl-, methyl-, ethyl-, propyl-, butyl- and other like alkyl-capped polyethylene glycol ethers of fatty alcohols; polyalkylene oxide free nonionics such as alkyl polyglycosides; sorbitan and sucrose esters and their ethoxylates; alkoxylated amines such as alkoxylated ethylene diamine; alcohol 5 alkoxylates such as alcohol ethoxylate propoxylates, alcohol propoxylates, alcohol propoxylate ethoxylate propoxylates, alcohol ethoxylate butoxylates; nonylphenol ethoxylate, polyoxyethylene glycol ether; carboxylic acid esters such as glycerol esters, polyoxyethylene esters, ethoxylated and glycol esters of fatty acids; carboxylic amides such as diethanolamine condensates, monoalkanolamine 10 condensates, polyoxyethylene fatty acid amides; and polyalkylene oxide block copolymers. Examples of particularly suitable water-insoluble, nonionic surfactants include ethylene oxide/propylene oxide block copolymer. Ethylene oxide/propylene oxide block copolymers as disclosed herein also include reverse ethylene 15 oxide/propylene oxide copolymers. A combination of various traditional and/or reverse ethylene oxide/propylene oxide copolymers may also be employed in the neutral cleaning compositions of the invention. In a preferred aspect of the invention, the ethylene oxide/propylene oxide block copolymer is a reverse EO-PO copolymer. In a further preferred aspect of the invention, the ethylene 20 oxide/propylene oxide block copolymer has a molecular weight less than about 10,000. Still further, in a preferred aspect of the invention, the ethylene oxide/propylene oxide block copolymer has water solubility less than about 1%. Commercially-available ethylene oxide/propylene oxide block copolymers include but are not limited to, PLURONIC@ products (BASF Corporation). 25 The water-insoluble surfactants are included in the neutral cleaning compositions in an amount effective to provide the detersive properties for effective cleaning. An effective amount should be considered as an amount that provides a concentrate of the neutral cleaning composition the optional detersive property. In an aspect the water insoluble surfactants are provided in the amounts of from about 30 1 wt-% to about 60 wt-%, preferably from about 5 wt-% to about 40 wt-%. 10 WO 2013/122934 PCT/US2013/025744 In a further aspect of the invention the water-insoluble Guerbet ethoxylate surfactant is provided in the amounts of from about 1 wt-% to about 10 wt-%, from about 1 wt-% to about 8 wt-%, preferably from about 1 wt-% to about 5 wt-%. In a further aspect the water-insoluble EO-PO copolymer surfactant is 5 provided in the amounts of from about 1 wt-% to about 50 wt-%, from about 1 wt-% to about 40 wt-%, preferably from about 5 wt-% to about 20 wt-%. Hydrotropes In an aspect of the invention and without being limited to a particular theory of the invention, the anionic hydrotrope is combined with the water-insoluble 10 surfactants to form a clear solution having stability at high temperatures. According to an aspect of the invention the hydrotrope provides clear stability at temperatures up to about 50'C and above. The combination is counterintuitive to one of skill in the art as the addition of the water soluble anionic hydrotrope is detrimental to the detersive microemulsions of the prior art. The combination of the anionic 15 hydrotrope forms a mixed micelle system resulting in a clear solution, destroying the microemulsion created by the combination of water-insoluble surfactants according to the invention. Hydrotrope usable according to aspects of embodiments of the invention include aromatic sulfonic acid, sulfonated hydrotropes such as Cl-C5 substituted 20 benzene sulfonic acid, naphthalene sulfonic acid, and the like, or combinations thereof. Examples of such a hydrotrope are xylene sulfonic acid, toluene sulfonic acid, naphthalene sulfonic acid, salts of xylene sulfonic acid (e.g., xylene sulfonic acid, sodium salt; xylene sulfonic acid, ammonium salt; xylene sulfonic acid, calcium salt; and/or xylene sulfonic acid, potassium salt; cumene sulfonic acid, 25 sodium salt; and/or cumene sulfonic acid, ammonium salt), salts of toluene sulfonic acid (e.g., toluene sulfonic acid, sodium salt; and/or toluene sulfonic acid, potassium salt), salts of naphthalene sulfonic acid, and the like, or combinations thereof. According to the invention, particularly suitable anionic hydrotropes are low molecular weight, water soluble agents. In a further aspect, suitable anionic 30 hydrotropes include low molecular weight carboxylates, optionally sulfonates. According to a preferred aspect of the invention, the anionic hydrotrope is selected 11 WO 2013/122934 PCT/US2013/025744 from the group consisting of xylene sulfonate and its salts, cumene sulfonate and its salts, and a C6-C10 fatty acid and its salts. A number of commercially available hydrotropes may be suitable for use in aspects of embodiments and/or embodiments of the present invention. Commercially 5 available hydrotropes may be obtained from a variety of vendors including, but not limited to, products under the tradename NAXONATE@. Additional examples of commercially-available anionic hydrotropes include sodium xylene sulfonate (SXS) and Colatrope INC, each of which are available from multiple sources. The anionic hydrotrope is included in the neutral cleaning compositions in an 10 amount effective to provide the stable, clear solution to overcome the water insolubility of the combination of surfactants according to the invention. In general, a clear solution is a composition having a clarity (e.g. absence of haze) similar to a composition containing only water. A clear aqueous composition further refers to a composition that is substantially free of haze. By substantially free of haze, it is 15 meant that one would not perceive the composition as hazy by simply viewing a 100 gram sample of the aqueous composition. According to the invention, an effective amount of the anionic hydrotrope should be considered as an amount that provides a concentrate of the neutral cleaning composition the optimal solution stability while maintaining a clear 20 solution. In an aspect of the invention the compositions retains phase stability at elevated temperatures, in particular at temperatures up to about 40'C, preferably up to about 50'C, and more preferably up to about 60'C. In an aspect the water soluble anionic hydrotrope is provided in the amounts (weight percent) of from about 1 wt-% to about 50 wt-%, from about 1 wt-% to about 40 wt-%, preferably 25 from about 5 wt-% to about 20 wt-%. As one of skill in the art will ascertain various suitable water soluble anionic hydrotropes are commercially-available in formulations having variable active levels which significantly impact the wt-% in the compositions according to the invention (e.g. SXS commercially available as 96% in powder form, 40% in solution, etc.). 30 In an aspect of the invention the weight ratio of the water-insoluble EO-PO copolymer surfactant to water-insoluble Guerbet ethoxylate surfactant is between about 2:1 to 20:1, preferably from about 2:1 to 10:1. In a preferred aspect the weight 12 WO 2013/122934 PCT/US2013/025744 ratio of the water-insoluble EO-PO copolymer surfactant to water-insoluble Guerbet ethoxylate surfactant is between about 4:1 to 7:1. In a further aspect the weight ratio of the water-insoluble Guerbet ethoxylate surfactant to the anionic hydrotrope is between about 1:20 to 5:1, preferably from 5 about 1:10 to 2:1, and more preferably from about 1:10 to 1:1. In a preferred aspect the weight ratio of the water-insoluble Guerbet ethoxylate surfactant to the anionic hydrotrope is between about 1:6 to 1:1. Still further the weight ratio of the water-insoluble EO-PO copolymer surfactant to the anionic hydrotrope is between about 1:10 to 10:1, preferably from 10 about1:5 to 5:1, more preferably about1:3 to 3:1. In a preferred aspect the weight ratio of the water-insoluble EO-PO copolymer surfactant to the anionic hydrotrope is between about 1:1 to 3:1. Accordingly to a preferred embodiment of the invention the weight ratio of the components of the neutral cleaning composition is between about 20:1:20 to 15 about 2:1:2, preferably about 10:1:10 to about 2:1:2, and more preferably about 6:1:6 to about 2:1:2 (EO-PO copolymer surfactant to water-insoluble Guerbet ethoxylate surfactant to anionic hydrotrope). In a further aspect of the invention the components of the composition may be provided on an actives level (without water in the composition). As one of 20 ordinary skill in the art will ascertain suitable amounts of water can be added to such compositions based on an actives level. In such an aspect of the invention the weight ratio of the water-insoluble EO-PO copolymer surfactant to water-insoluble Guerbet ethoxylate surfactant on an actives level is between about 2:1 to 20:1, preferably from about 2:1 to 10:1, and most preferably from about 4:1 to 7:1. In another 25 aspect, the weight ratio of the water-insoluble Guerbet ethoxylate surfactant to the anionic hydrotrope on an actives level is between about 1:10 to 1:1, preferably from about 1:5 to 1:1, and more preferably from about 1:3 to 1:1. In another aspect, the weight ratio of the water-insoluble EO-PO copolymer surfactant to the anionic hydrotrope on an actives level is between about 1:5 to 5:1, preferably from about 1:3 30 to 3:1, and most preferably from about 1:1 to 3:1. Optional Functional Ingredients 13 WO 2013/122934 PCT/US2013/025744 According to an optional embodiment of the invention, additional functional ingredients may be added to the neutral cleaning compositions of the invention. The compositions may include additional components or agents, referred to herein as additional functional ingredients. For the purpose of this application, the term 5 "functional ingredients" includes a material that when dispersed or dissolved in a use and/or concentrate solution, such as an aqueous solution, provides a beneficial property in a particular use. In an aspect of the invention, the compositions may further comprise, consist of and/or consist essentially of a preservative, colorant, fragrance, viscosity 10 modifier, organic solvent, antimicrobial agent, alkalinity source, chelating agents, pH adjusters/buffers, foam modifiers, pearlising agents, stabilizing agents, rheology modifiers and/or combinations thereof. In an aspect of the invention, no additional functional ingredients are added to the neutral cleaning composition. In a further aspect of the invention, no 15 defoaming agent is added as a result of the low-foaming profile of the neutral cleaning composition. In a further embodiment of the invention, no viscosity modifier is included. In a still further embodiment of the invention, no builder, chelant, sequestrant and/or threshold agent or inhibitor is included. Still further, in another embodiment, the neutral cleaning composition does not contain an organic 20 solvent. Optional functional ingredients may be included in the neutral cleaning compositions in an amount effective to provide the optional functional properties. An effective amount should be considered as an amount that provides a concentrate of the neutral cleaning composition the optional functional property. In an aspect 25 the optional functional ingredient(s) are provided in the amounts of from about 0.1 wt-% to about 50 wt-%, preferably from about 0.1 wt-% to about 20 wt-%. Water Water can be added to the detersive neutral cleaning composition concentrate to form the detergent composition use composition. In general, the use composition 30 refers to the composition that contacts a surface or article to provide detersive activity. It can be advantageous to distribute the neutral cleaning composition in the form of a concentrate, and then dilute the concentrate with water to provide a use 14 WO 2013/122934 PCT/US2013/025744 composition at the situs of use. According to the invention water can be added to the concentrate to provide a use composition having a dispense rate of from about 0.1 oz./gal to about 10 oz./gal, preferably from about 0.1 oz./gal to about 6 oz./gal, more preferably from about 0.1 oz./gal to 4 oz./gal. 5 The neutral cleaning composition concentrate can be provided without water or it can be provided in a form that contains water. The concentrate can be provided as a powder, a solid, a gel, or a liquid. When the concentrate is provided in the form of a powder, the concentrate can contain about 0 to about 10 wt-% water, about 0.1 wt-% to about 10 wt-% water, or about 0.2 wt-% to about 5 wt-% water. When the 10 concentrate is provided in the form of a solid, the concentrate can contain about 0 to about 50 wt-% water, about 5 wt- % to about 30 wt-% water, or about 10 to about 25 wt-% water. When the concentrate is provided as a liquid, the concentrate can contain about 20 wt-% to about 90 wt-% water or about 25 wt-% to about 80 wt-% water. In general, the concentrate can contain water in an amount of less than about 15 90 wt-%. Above 90 wt-% water, the neutral cleaning composition tends to look more like a use composition. It should be understood, however, that the weight percent solids in the use composition can be adjusted to provide a desired level of detersive activity. In certain circumstances, it may be desirable to provide a use composition having a solids content that is less than about 5 wt-%, less than about 3 20 wt-%, less than about 1 wt-%, less than about 0.5 wt-%, or less than about 0.1 wt-%. Kits According to a further embodiment of the invention, the neutral cleaning compositions of the invention can be packaged and provided as a kit for hard surface cleaning. According to an embodiment of the invention, a kit may comprise, consist 25 of and/or consist essentially of the neutral cleaning composition according to the invention, a container, and suitable instructions for use. According to a further embodiment, the kit may also include a removal agent for removing a plurality of soils from a treated hard surface. Suitable removal agents for use in applying the cleaning compositions for 30 removing a plurality of soils according to the invention include but are not limited to: a scrubber, a mop, a roller or a spray. Examples of suitable scrubbers include 15 WO 2013/122934 PCT/US2013/025744 manual and auto floor scrubbers. Examples of suitable mops include string and flat mops. Methods of Use An embodiment of the invention includes a method of using the neutral 5 cleaning compositions to clean hard surfaces, particularly architectural surfaces, particularly floors. The methods of use are suitable for both indoor and outdoor applications. The methods of use of the neutral cleaning compositions may be employed on a daily or weekly basis for cleaning. In a further aspect the methods of use of neutral cleaning compositions may be employed on a less frequent basis. In 10 one embodiment, the composition is applied onto a surface at least about 3 days a week. In an alternative embodiment, the composition is applied onto a surface once a day. One of ordinary skill in the art will ascertain the various application timings according to the invention. The methods of cleaning a surface may comprise, consist essentially of or 15 consist of applying the neutral cleaning composition to a hard surface, and allowing the hard surface to dry. A surface treated with the composition generally dries within about 1 hour of when the composition is applied to the surface. However, the amount of time it takes a surface coated with the composition to dry depends on the method used to apply the composition and the environmental conditions. A surface 20 treated with the composition may dry within about 30 minutes, about 15 minutes, about 5 minutes and about 1 minute of when the composition is applied to the surface. For example, if the composition is applied with a mop and bucket, the surface will dry within about 5 to 15 minutes. If the composition is applied with an auto scrubber, the surface will dry almost immediately. 25 According to a further embodiment, the method comprises, consists essentially of or consists of applying to a hard surface a neutral cleaning composition comprising about 1-10 wt-% a water-insoluble Guerbet ethoxylate surfactant, about 1-50 wt-% of a water-insoluble EO-PO copolymer surfactant, about 1-50 wt-% of a water-soluble anionic hydrotrope and about 20-90 wt-% of 30 water, wherein the composition has a neutral pH and forms a clear solution. The methods may include a step of first diluting the composition into a use solution with water before applying the composition to a hard surface, and wherein the dilution 16 WO 2013/122934 PCT/US2013/025744 provides a dispensing rate of a use solution of the neutral cleaning composition from about 0.1 oz./gal to about 10 oz./gal, preferably from about 0.1 oz./gal to about 6 oz./gal, more preferably from about 0.1 oz./gal to 4 oz./gal. The neutral cleaning compositions according to the invention may be applied 5 to a hard surface using a variety of well-known application techniques. Suitable and non-limiting methods of application include mop and bucket, auto scrubber, flat mop, string mop, spray dispenser or other conventional application methods. A surface to be treated according to the invention may be further treated using additional cleaning agents, rinse agents and/or polish agents or solvents that will be 10 familiar to those skilled in the art. The methods may optionally include a rinsing step to remove any excess neutral cleaning composition. A rinse step may be used alone or in combination with a further step for removing soils from the hard surface, e.g. applying a water source and/or mechanical force to remove soils. For example, the use of non-traditional 15 mechanical force, such as compressed air or a vacuum can be utilized to clean the treated hard surface in combination with the neutral cleaning compositions. Additional treatment steps may be employed in combination with the invention. Without being limited to a particular combination of surface treatments suitable for combined use with the neutral cleaning compositions, exemplary 20 treatments include application of compositions for additional shine, non-slip, polish, polish restoration or the like. The methods of use according to the invention are suitable for cleaning or treating a variety of hard surfaces, particularly architectural surfaces, particularly floors. Suitable substrate materials often used for flooring including marble, granite, 25 other stone surfaces, terrazzo, concrete, dry shake, ceramic tiles, wood, laminate, linoleum, vinyl, cork, bamboo and rubber substrates. Flooring surfaces described herein are understood to include both coated and uncoated floor surfaces, and further porous or non-porous floors. Additional suitable hard surfaces for application of the neutral cleaning 30 compositions according to the invention include a variety of soiled surfaces. Exemplary soiled surfaces include architectural hard surfaces, such as toilet bowls, baths, showers, other plumbing fixtures, bathroom and kitchen hard surfaces (e.g., 17 WO 2013/122934 PCT/US2013/025744 countertops), glass windows, and vehicular surfaces. One of ordinary skill in the art will ascertain from the disclosure of the invention the various suitable hard surfaces that would benefit from the methods and compositions of the present invention. 5 All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated as incorporated by reference. 10 EXAMPLES Embodiments of the present invention are further defined in the following non-limiting Examples. It should be understood that these Examples, while indicating certain embodiments of the invention, are given by way of illustration 15 only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the invention to adapt it to various usages and conditions. Thus, various modifications of the embodiments of the invention, in addition to those 20 shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. Various materials are used in the following, non-limiting examples. Additional description of these materials and preferred ranges and ratios of the 25 components for concentrated compositions according to the invention are provided below in Tables 1A-IC. TABLE 1A Material Tradename Description Vendor Water-Insoluble Ethoxylated 1 Surfactant (Guerbet hydroxy-2-propyl ethoxylate) Lutensol XP-50 heptane BASF Corp. Water-Insoluble secondary alcohol Surfactant Tergitol 15-F-7 ethoxylate nonionic DOW 18 WO 2013/122934 PCT/US2013/025744 Material Tradename Description Vendor Water-Insoluble Ethylene Copolymer Oxide/Propylene Surfactant Oxide Block Pluronic L61 Copolymer BASF Corp. Water-Insoluble reverse (i.e. PO Copolymer terminated) ethylene Surfactant oxide-propylene oxide copolymer Pluronic N3 surfactant BASF Corp. Hydrotrope sodium salt of ring Sodium Xylene sulfonated mixed Sulfonate (SXS) xylene isomers Various Hydrotrope Isononanoic Acid, Colonial Colatrope INC sodium salt (1:1) Chemical Preservative Chloro Methyl I Kathon Isothiazolin mixture Various TABLE lB Component Range 1 Range 2 Range 3 (wt%) (wt%) (wt%) Water- 1-10 wt-% 1-8 wt-% 1-5 wt-% Insoluble Surfactant Water- 1-50 wt-% 1-40 wt-% 5-20 wt-% Insoluble Copolymer Surfactant Hydrotrope 1-50 wt-% 1-40 wt-% 5-20 wt-% Water 20-90 wt-% 30-90 wt-% 50-90 wt-% Other 0.1-50 wt- 0.1-20 wt- 0.1-10 wt-% Ingredients % % 5 TABLE IC % by wt Components Ratio Water-Insoluble Copolymer Surfactant (EO-PO polymer) to Water-Insoluble Surfactant 2:1 -20:1 2:1 - 10:14:1 -7:1 (Guerbet) Water-Insoluble Surfactant (Guerbet) to 1:20 - 5:1 1:10 - 2:1 1:10 - 1:1 Hydrotrope Water-Insoluble Copolymer Surfactant (EO-PO 1:10 - 10:1 1:5 - 5:1 1:3 - 3:1 polymer) to Hydrotrope 19 WO 2013/122934 PCT/US2013/025744 Active Components Ratio Water-Insoluble Copolymer Surfactant (EO-PO polymer) to Water-Insoluble Surfactant 2:1 -20:1 2:1 - 10:14:1 -7:1 (Guerbet) Water-Insoluble Surfactant (Guerbet) to 1:10 - 1:1 1:5 - 1:1 1:3 - 1:1 Hydrotrope Water-Insoluble Copolymer Surfactant (EO-PO 1:5 - 5:1 1:3 - 3:1 1:1 - 3:1 polymer) to Hydrotrope EXAMPLE 1 Neutral cleaning compositions according to the invention were formulated to 5 achieve a low foam formulation, and comply with low toxicity requirements (e.g. GS37 Standard and/or Green Seal compliant). The compositions were concentrated at an appropriate level to provide acceptable cleaning at a 0.25 oz/gal dispense rate. The neutral cleaning compositions were compared to various cleaning compositions that are commercially-available. 10 Commercial Product A is a commercially-available, daily use neutral floor cleaning composition, providing a negative control for various cleaning experiments. Commercial Product A has a recommended cleaning concentration of 0.5oz/gal - 1.0 oz/gal. Commercial Product B is a commercially-available, daily use neutral floor cleaner with a daily use recommended cleaning concentration of 0.64 15 oz/gal or 0.50%. Commercial Product C is a competitive, daily use neutral floor cleaner with a daily use recommended cleaning concentration of 0.25 oz/gal - 0.5 oz/gal. Commercial Product D is a commercially-available, daily use, alkaline floor cleaning composition with a daily use recommended cleaning concentration of 0.25 oz./gal. This product is not a neutral composition, providing a positive control for 20 various cleaning experiments and was tested at a 0.5 oz./gal cleaning concentration to further test the cleaning efficacy of the neutral cleaning compositions of the invention. The cleaning ability of the various neutral cleaning compositions at the maximum allowable concentrations, complying with the toxicity limitations was 25 evaluated. The toxicity limitations apply to the concentrated product. The maximum active level of the concentrate was first calculated. From there, the use active level was calculated based on a 0.25 oz/gal dilution. Concentrates were 20 WO 2013/122934 PCT/US2013/025744 prepared at a 19% active level so the dilution level of the concentrates was adjusted to provide the desired use solution active levels. Table 2 shows the maximum concentrate active level (%) allowed for compliance of toxicity limitations set forth in the GS37 Standard. 5 TABLE 2 Maximum Concentrate Active Level (%) Use Dilution Use Dilution Allowable for Active Level w/ Active Level w/ Toxicity 0.25ozgal O.25oz/gal Cocnrt D Limitations Dilution (%) Dilution (pm) C116% 3.13% 313 02 21% 4.10% 410 03 29% 5.66% 566 04 16% 3.13% 313 05 21% 4.10% 410 06 29% 5.66% 566 07 16% 3.13% 313 08 21% 4.10% 410 09 8% 1.56% 156 10 Table 3 shows various concentrate formulations according to the invention. Table 4 shows the various use solution preparations according to the invention. TABLE 3 expressed in % by wa-t Raw Material Descripion C1 C2 C3 C4 C5 C6 C7 CB Water 81.02 81.00 81.00 81.00 81.00 81.00 81.00 81.00 Lutensol XP50 6.02 4.00 2.00 6.00 4.00 2.00 6.00 4.00 Tergitol 15-F-7 12.96 15.00 17.00 0.00 0.00 0.00 0.00 0.00 Pluronic N3 0.00 0.00 0.00 13.00 15.00 17.00 0.00 0.00 Pluronic L61 0.00 0.00 0.00 0.00 0.00 0.00 13.00 15.00 Desired Use Active Level 3.13% 4.10% 5.66% 3.13% 4.10% 5.66% 3.13% 4.10% 15 Dilution Level 0.16% 0.22% 0.30% 0.16% 0.22% 0.30% 0.16% 0.22% 20 TABLE 4 21 WO 2013/122934 PCT/US2013/025744 Expgrimental Test JD Concentate ID g Cpncentrate g Water % by wtL cg EXP1-1 01 0.81 499.21 0.16% EXP1-2 02 1.11 498.94 0.22% EXP1-3 03 1.50 499.74 0.30% EXP1-4 04 0.80 499.21 0.16% EXP1-5 05 1.15 498.85 0.23% EXP1-6 06 1.55 498.44 0.31% EXP1-7 07 0.79 499.20 0.16% EXP1-8 08 1.10 498.92 0.22% EXP1-9 09 0.35 499.64 0.07% EXP1 -10 Commercial Product A 1.96 499.20 0.39% EXP1 -11 Commercial Product B 0.99 502.63 0.20% EXP1 -12 Commercial Product C 1.00 499.00 0.20% EXP1 -13 Commercial Product D 1.95 498.34 0.39% EXP1-14 water 0.00 500.00 0.00% EXAMPLE 2 5 The neutral cleaning compositions according to the invention and the Commercial Products according to Example 1 were evaluated for soil cleaning efficacy. Soil Application Procedure: Black oily soil was made by mixing the approximate amounts of the following materials: 50 g Mineral Spirits, 5 g Mineral 10 Oil, 5 g 10/30 W Motor Oil, 2.5 g Oil Dag, and 37.5 g Bandy Black Clay. Cleaning Procedure: Four coupons were cleaned per condition tested, using 5-grain tap water as a control. The coupons were placed in the tray and ~200 g of the cleaner/dilution was added. The coupons were allowed to sit in solution 2 minutes before cleaning. After adequate dwell time, a sponge was placed in the PFA, and 15 cleaning begun. The normal force before each cycle was set to 2 lbs. The black soiled coupons underwent four sets of 10 cycles (20 passes x 4 sets) each. Two coupons were tested per PFA run. Data Analysis Procedure: After soiling, 10 measurements of the L, a, and b values of the coupons were taken at random. After cleaning, 5 measurements of L, a, 20 and b were taken per coupon, and the averaged values as well as their standard deviation were considered. After soiling the coupons, they had a very similar color values. One set of five coupons had an L value of 27.92+/1- 0.49 and a second set of five coupons had an L value of 28.05 +/- 0.29. The after clean color data is below in Table 5 (After Clean Color Data) and further depicted in FIG. 1. 25 22 WO 2013/122934 PCT/US2013/025744 STABLE ,\\I** *\'k\' I 11\*Vt\'k\ , ......................................................... ......................................... ....................................................................................... ......................... .................. ......................... ...................... ::*::*::*::**:******.*.****:**:*******:*:*:*:*:*:* :*:*:*:************:****:***- ----------- '---------.-.-.-.-.-.-.--.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-..... .................................................. .................................... ................................................... ............................................ ................................................ .: :::: ::::: : . .:::::::: :::: - *- * .:::::::: ::::. -* .* " : :.............. ............................................ ................................................ ..: ::: :::::::: ... - .:::: :::::::: - .:. . :::: :::::::: :..: : ....... ...................... ........................ ...... :E . . ... A . ... .. ... ........ ... :. .......................................................... ...... - 3 .. :. :.......:.......... : : : : : : : :T : : : .. A ::.:.:. : : : : : : : :o -. O . : : : : : : : :: : : : ::.7 :::::::::::::: ....... ...................... ......................................... : .X .P .:.l: i -1: : : : : : : : : :*....-...*6 .4.1..9 :-:-:-::-:-:-:-: ........ 6 5 0 2 ...... . . ........ ........ .... ........ .... ............ .............. 9 ....... I X ... 2 : 1 .............................. V ..... ... :.:.:.:..:.:.:.:.:.:.:.Q :...Q -.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-................... .... ................. ............................................ ......................... .................. ................................. ............................................ ................................................ ,,,,- ...... ... ............. ....................................... ............................................................................... ......................... .................. ................. " ...... ............................................ .............................................. ............................. .................... .................................................................... .................................................. ....................................................................................... . .. :::::::: .*..* : :**** :::::: :::: . ........ . ..... ........................................... ................................................ .... *2 . .... ........ ... .:::::::: :::::::: - * * .. * *.:::: ::::::::a :..: : :........... .................................... .............................................. . . ::::: .. :::: :::::::G ... . ::a : . ..... ........ .. ... ..... ... .. ........ ........ ..... . ....... ........ ........... ........................ .. ........... ...... ]Q .1 . .6 : .: : . . . :::::::::::::: ........... ...................... :::.E :T .. I :::::::::::-..-'....-'. '-- .... ::::::::::::: :*. . -* -. .:::: :::::::: *- .. :::::::::::: -* - . ....... :: X .P . . :::::::: :::::. ........ .............. .. ............... .......................... .............................................. .. . *.*:::: ** . ........ ................ ... * .......... ......... ........... .:.:.:.:.:.:.:.:.:.:.:-:- .N. . ::::::: -. '2 ::::::: :::::::::::::: -. .A . . . . .. .. ::: ... * .. .... .... : I S . ::::::::: 0 5 .0 3 :::::::::::*** ***** 1 . 5 : 1:6 ...... .. ...... ......................... ........... ,.: :.:.:.:..: ....... :.:.:.:..:.:.:.:.:.:.:....-.................................................................................................................. .. ............ ............. .................................. ......................................................................... . ..... ................... ......................... ...................... ........................ .. ........................................................................................................................................................................................................... :::::::: .. :-.-. .t :::::: :::: .. :::: :::::::: : ::::::::: :::: ............. :::: :::::::: ................. .................. ......................... . *.*.*.............................. ................................................ :::C .. . :*.*. :::::: :::: ** - ' ........ .. ::.3 . : :..: : .. :::: :.. :::: .. .. - ... . . . .. . . ......... ............. .. ....... ........................ ........................ ... : :........... ... .... .............. ....... ... ....... ........ ... ............... ... .......... ............... ... : ... . .. ............... ....................................................... ::: .. X :1 : ........... --1:9 :::: ::::::::I:* .. . ...... . .......... .... .... .. : : : ........ :.,. :.::::::: :T --- :2 ---------- -D . :::::::: :::::::: -*-*-*-*-*-*- *-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*- *-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-* : .... ** *: : -:-:-:- -:-:-:- - 4 ::::::::::::I :" .. 7 -..- ::::::::::::D :: :.9 .':******* ........... .... :: ........... .7 . . O .. .................... o . : ::::: .R :.. -. .. .. - .1 ..... .:.:.:.: : : 6 : :**I:: * .. ...................... ....................... .. . . . .... ...... .. ....... ':':': :-:-:-:..X ...... :-:-:-:.-:-:-:-:-:-:-:-...x ...... :-:-:-:-:-:-*-* .*.*.*.*.*.*.*.-.-.-.-.-.-.-.-......- ........................ .. ................................................ ............................ ............................................................................... ......................... ........................ ............. ........ .................................... .............................................. .. ............. ............ ................... ......................... .......................................... ........ .. ... . .... ::::: . .... ...... .. .. .... .... . .... .... ........ . ...... ... .. ... ......... .. . ...... .............. ........ ..... ... .... .... : *..*..*..*..*..* *** ... ....... ................. ..... ... ... .... ............... .. ........................ .. ............... ........... ... ..... ..... :::: :::::::: :*. 0 ::::::::::::::l . ::.. ::::::::::-S -- * ... k 2 a ........ ... .. ::::E P . . .... ........ .... .......... ...... . : : : ******* ... ....... ::.:.:.:.:,.:.::: :::: .:.:.:.:.:.::::O io ::::::::::::::::.:.:.:. - :-:-:-:-:-:-:-:-:-:-:-: - -:-:-:-:-:-:-:-:-:-:-:-: .- :-: .. *..:.:: ........ .............. :: ... :.l:: ..- 'I*.::::::: :::: 6 -*'-2 .. 4 -'*.:::::':':':'::::::::-I:::::6 *.:5 **.::::::::::::::::::::::::.O ::: -.-.. .::::::::.: ............................ .......... I ........ :.:.:.: .:.:.:.:.:.:.:.:..:. :...:..:.:** '* 6 :::.:.:.:.:.:.:.:.::-I :. ':..-'I::4 ::::::::::::O ::I::'B :':':':':':':'::':':':::3 7 :::9 *6 :::::::::::::::::::::::.I ::::7 ..************** ****** ****************** ******************* .......................................... ...................... ........................ EXP1-2 43.98 1.32 0.31 0.04 2.02 0.18 EXP1-2 43.07 1.67 0.32 0.04 1.97 0.16 EXP1-2 42.23 1.12 0.39 0.06 2.03 0.30 EXP1-2 44.34 0.74 0.48 , 0.05 2.72 0.06 43.21 , 1.06 ......................................................... ......................................... ....................................................................................... .................................................. ................................................. X : ............................ -.-.-.-- - -- - - - .. . .... .... - .......... ....................... . . .................. ... .... .... - ::::::: ::::::::::::::: *.:: E . :: * . :::: * ........ * . ....... .... ....... . - .1 :** ........ . .............. :.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:............. ......................... ........ ... .... * : ***** * ....... ...... .' .................... .. ............... ............................................. ........................................ :.:.:.:. ...... . ..................... .................... :::: E :*-t : : : : : I : : :a ........ . ... . .:.::::::::::::..:..* - :.:.:.:::: ... :: :.*. ... :1::::::.::.::.::.::.::.::.::.O *.: 0 4 :-:*-**.**.**.**.*.* .**.**.**.**.**.**.**.**.**.**.**.**.**.**.**.**.**.**.**.**.**.** .*********************************************** x...... I .'-.'.' - .:.:.:.:.:.:.:.:.:.:.:..*..*,: .* .::::::: :::. j 3 .... ** - .::::::: 1: .. :..:..:..:..:: *X *P -: :*. 3- :::::::::: ... 7.....**...7..:.2 :::: :::::::::::.O *:::6 .. a ::::::::::::::::::::::::*O *.:::.* 0 *.:....... .0 :0 4 ::::::::::::::::::::::.::: 4 : :::::: : ................................................................................................ .... .......... ............. .............. .::::::.::.i.: .. :;..:..::.............. ...................... ......................... A . .... ...... - ...... ...................... ................ .. ............. ............ .................................... ....................................................................................... .................................................. ................................................................................. ...................... ........ **************** ::: . ::::: . . ::: ::::::::::*::::: .::::::::::::::::::::::::. :::: ::::::: *-.. ::::::: .............. ............................. ........................................ ::::: .: ::: .. .... ...... . I .. ....... ...................... ........................ .... ........ ...... ** .... *** . ........ ..... .. .............. .. ........ .................. ... 1 : ::::: :::.. ... ........ ................. ... .... .... ... ::::: ... o ....... ..... .. ...... . ....... ....... .......................... ................................................ ..... :. : :::::: . ..... .. .. ::::::: ::::: .: .*i... ........... :..:::E -'.X '..-'R :.:.'-.'.'-.".'.:::::::::: a *.*.6 *.: . 0 7 .. :.:.:.: ..... ..... .. ........ *************** ....................................... ....... . . . . . : ..... :.:.:.: ... X................... *.3 .*.**:::: :::::::: ** 8 1:::::*;$ , *.::::::::::::::::::::::::O *.:::.2 .. 2 .: ::... .. - Q . 3 .. *..*.**O .. M ::0 2 -:-:-:-:.:.:.:.:.:.:.:o -:-:-:-:-:-:-:-:-.:-N-..-. *.*.*.*..*.*.*.*.*.*.*.* . :-:-:-:-:-:-:-* .*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.* .*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.* .:.:.:.:.:.:.:.:.:...:,......: .... *****..*** ....... * *:::::::: ::::::::: * *3 ** ....... ...................... ...... ......................... ...................... ........................ .. ............. ............ ...................... .................................------- .................. ......................... ..................................................... ...................... ........................ ............ ............................................ ......................... .................. ......................... ...................... ........................ . :: .. - ****:.:.:.:.:.:.:.:. *:*. . .. :.............. .'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.'.- .'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'-'- S ' .. .... .... ........ .. .......................................................................................................... :::::: .. *.** -- : :' -'S :::::::::: **D .*.:::: ::::::::.:*. :::::::::::: .4 77 : .... ..... -. 0 - ............................................................................................................ : .. -* :.** *0 ... *. .. ' :::: :::::::: * 5 --* --:::: .......... -T :: : : : I : :A .Q *--,-- : : : : : : : : : :.:.: :.. ::::::::::::: ..-.. :::::::::::: .... .7 . ..... .. * * .. -** *: :.. 4* .: : : : : : : : : : :& - * : : : : : : :4 : :::: *,*2 :::::::::::::::::::::::: :**. -:-:-:-:-*-*-* .*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.* .*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.* ..... - .... : .. ,., ... .9 :::: 4 .... :::::::::::: . ::::::E X...P........... ... I. .... ........ 1. .:.:.:.:.:.:: : .. !R .. ............ w o : ... ............................................................................................................................................................................................................................................................. - -- - - - - - -............ ............................................ ......................... .................. ...................... ............................ ..................... ......................... .................. ......................... .......... *********************** ****** ******************************************** ************************************************ :*::**::**:**************:*****:*:*:*:**.* ******************* ............................................. .. :- -::.:.:::.:.: ... * .............. ..... *..:.: ...... *.:.:.:.*:.:.:.:.:.:.:.:..O .. :..:..:.*.*.*.*.*.*.*.* ... ........... * ........... .............. * .......... .... .. :::: :::: ... O : : . : ::::::::.. . . . . . X . ........... . .. ... .. . :::.:.:.:.:::*: ::::: :*. . ::::: . ::::: :::::::: . : ...... ..... .......... ... ... .......... *--*' o ..... . .... ............ ... ........ ..... ..... .... .. . . . :. : :.......... ............. :.... : ... . - ... ::::::. : .. .. .. .. ::: ** ** ** - **** ******** - - . .. .::*:*:*:*:::: :::: ......... : : **:::::::::::::::::::: .*2 ........ : -:-:-:-:-:-:-:- -:-:-:-: ' ' 2 ............ ....... 1 : - --5 :::: :::::::: *- .--. - '-..7.- ::: ::::: -X .:.:.:.:...... - :..:::::::::::::: 9 *:4 : :..:..:..:..:..::::::::I : .. ' ...... .. : . ... Q .7 :::::::::::::: ..- :::::i:::::::::::::: .... . .: . ....... ............. ...... . .. ... S...........4. * Y 9.3.:::::::::::: Q * . 0. .3 ..... :.........I. 59 :31: a I ...... ".3 ::::::E -- X------'P -::* -. *:::::::::: ....... :-:-:-::-:-:-:-:-:-:-...-X ....... * ....... .................. ;...*..::::I: .. ...... **** ........ ......... ....... ........... ......... .............................. ...................... ....... .............. -- - - -- - - -- - - -............ ............................................ ......................... .................. ......................... ...................... ........................ ............................................................................................................................................................................................................... :::::: x ... : ............. .. .................. ............................................ ......................... .................. ......................... ...................... ........................ . : .. ... ................. .................................. . .. .. .:.:.:.::::::::::I 2 *:::::::: :::::::::::::: .. . .............. ...................... .. . :::::::: , : : : : ....... : .... ** * * *3 ***.0 8 .......................... ::::: ::::::::::::::::::::::::.O *.::: .8 :: *- : ::::::::::::: *:.* *: *** - ...................... ....... ... * .. .. * .... iiij. j.::R :::::::j:j:j:j:j:j:j:j: :: : : : :E . .. P :j i i i i i i .. .... .. .i*.4 . . . : . .. ....... ***** ******* ....................... ... : .. : : .... -*-- -* i A :::: 3 3 .*::.*.*.*.*.*..*.*.*.*.*-*- . .*.*.*:: 0 ... .I .............. 1 :- 8 :-:-:-:- -:-:-:-:-:-:-:-:a : 0 .* * * * * * * * * * * *................ ................................................ ........ ........ ......... ..... ::*:*:*:*:*:*:*:*:*::.:.:.:.:.:.:.I:*********************** .. ....... ...... ..... :.:.: :::::::::::::: M . . : .. X...................... .:.::.: .:.:.:.:.:.:.:.:..:. :..-....:.:..:.:.:.:.:- -:-:-:-:-..X ... : : .... ........... * *- I .... ....... ......................... ...................................... .. ............ ............. . ...................................... ................................................... *.*.:.:.*.*.* .......... :.:.:.:.[: ...................... *.*.*. ........................................... *.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*... ............................................ ................................................ ... ... * * * .... :::::::: ... .e : ...... ...................... ............................................... ::: -- i i .. ... ... *- :::: :::::: * .... .. .. ............... ............................................ ..... -----...................... - ....... ...................... ................. ......... .. *** - * . ........ .. ........ ...................... ........................ .. ... . . ... ........ .. ...... ............. .... . .... ....... .. ........ ...................... ........................ :::*A= .1 i i.i.i.i.T .i.4 .. .. .... - :::::::::::: -. *- ::::: :2 . " ****** ************** ******* ************************ ..: ::::::::: :i......:..*.* *::::: :i..*. ::::::::: :::: *A -2 ........ :-:-:-:-:-:-:-: . ................ ............................................ ................................................ :::::: *** ***. .*-*-* ::: :::::::::::::-I::::-4 -'...-::::::::::::::::::::::':': ::: ... *.:::: :::::::::D .::*O .. *-....-..:::::::::::::::::::::::.2 .::*o .*::::::::::::O : .:.:" .... ::: . .. .- l****.:.:.:.:.:.:..:.:.:.: I ... ...................... ........................ ..... ::::::::::::::::: .... I 0 . :::::::::::****** * * * * ******** ***** .:.:.:: .- X -.- **...P...*.:: .4 -**.:::::::::. .6 **.7-.*...7-.-**.: 5 . *.7 .* ........................................................................................................................................................................... -- - - -- - - -- - - -............ .......................... .... ......................... .................. ... . ............................ ..................... ................. .... :::: .... ... :::::::: :::: ****** ****** ... :.:.:.:. ......................... .................................................................. ............................................ ............................................... * . ....... ...................... . . ..................................................... ... * .... ... -- -:-:-:-: :::: :::::::D .. . .... ........ .. ....... ...................... ........................ . :::::::::::: :...- . :::: ... ....................... O ..- 7 .- 6 -:-:-::-::-::-::-::-:::::: : *: .... . *.*.::::: .. ::::::: .. -1 .:.:.:.:..:.:.:.:.:.:.:.: :. .:.:.:.:.:.*.*. ............................................ ............................................... -:-:-:- :-:-:-:-:-:-:-:..*.i.:..:..*'. ::: .:.:.:::: .. * . * .0 ..:**** * *7 ........ ........................ ........................................... .. :.:.:i:i:r-' J -i -i.i.i.i.i.i.i.i.-.4 **.**.****.4 -- 2 .:::: ::::::::::::* I .* ...... :::,:: ..... ::::::::::::::::: .... 4 .**. ' '::: . .I io .:.:.:.:.:.:.: :.:.:.: . I : ............ .,a : ...... ........ . 6 .:::: :::::::: ** 3. .::::::::::::.2 .** :.:::::::::::::: 0 : 0 ... *...*.: * * * * * * * * * * * * * * * * * * * * * * * * * * * * * ********************************************** :,:,:,:,:,:" ..- X -.-. 'P .. ': : -'4 -. '.::::: :::: .0 ::: 1: .... ......................................... .............................. ............. ......................... .................. ......................... .......................................... ............. ............. .................... ................................ -- - - -- - - -- - - -............ ......................... . . .. .................. ......................... ...................... ........................ ............................ ..................... ................. :::::::: :.:.:.:.******.******............. ................................................ ............................................ ...................... ........................ ::::::: -.-. *.* *: :4 : **** ** * . .... ... * . .::::::: x iii .i iiiiiiii .i.i.i.i." .. 3.*:.I:::*:*:*:*::.:.:.:.:.:.:. :.*.. :..*.:.*.*.*.*.*.*. . . * * ... .... ... : 11 .:.:.:.: i i i i i i i i :i .. :::: :..** :::: ... ........ ........ .. .. .... * - .... .. ....... .... . ........ . . . . . ..... :: :::: ... .... . ..... ....... .. ........ :-:-:*- -*. ... .. : ... i.i.i .ii.j .......... 1. ........ ... *.*.:::::::::. -* -* * * * * ...... :::::::: - ::..... ............ ::::.:*i-r- .X ......- I.i .*i*i: iiiiiij. , - .. ................ ...... ..... . 5 i:::: ... :::::: :::: * ** . .. .:::.:.:.:.:.:.:.:.:.:.:. ..... ........... ... ,-8 .. ... X-:4.: -:-:-:-:-:-:-:-:-:-:-:-:-: ...... :-:-:-:-:- ,-,.,.,. -, .... ,.,.,.,. .1.1.1.1 ..... P .A.: .:.:.:.:.: .:.:.:..4 .... **.9 .. *6 .. .*.:::..7 ... *. .. :::: : 4 1 2 .. .3 .:::: ::::::::::::O -*...5 -:-:- .:.:.:.:. *:*:*:*:.jD *::: 5 .:::: ::::::: G 0 *. :.:::::::::::.I :**. .i.D *::::::::::::O :: :*.i:::::::::::::: **. .:..: . . . ............. .................. ........ V .... :.:.:.: -************************* ****** .................................................. ................ EXP1-5 49.71 1.12 0.41 0.03 2.37 0.05 EXP1-5 47.76 0.59 0.31 0.04 1.78 0.13 1 EXP1-5 47.36 1.90 0.36 0.04 1.98 0.16 EXP1-5 46.04 0.76 0.31 0.03 1.72 0.24 47.72 1.52 ............................ ......... -- - - -- - -- - - --- --- - -................... ............................................ .................... -- - - -- - - ............................. ........................ .............. *.***::::::::::::::::::::***.*** ....... ......................... .................. ......................... ...................... ........................ :::: ::::: : : - . . .. ... .. :::::: *:..: : .*.:.*.*.*.*.*.*.* .*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.* .*.*.*.*.*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-* 2 * ................. ....... .... ........................ ... .. ................ ............................................ ................................................ ' ' .. : ..:::: :::::::: . .. .. ::::::: .. * ... ::::::::::::::: ::::::::* : '* -- " .. :.:.:.:.:.: .: * ::::: :::-***.-*... . ....... .......... * 7 ... . 5 . ... ::::: :.:.:.:.:.E .. ) : :-* *** ::.:.:.:.:.:.:.:.: .. .. : : .. ::::O .. ,.*.*. :::::: :.......... .(-.P.:.l:*'*' ::::::::::.4 .-. .. & ... :j:j:j:j:j:j:j:j . ... *:::::::::::: *ffl . .:6 OX.3 .... ::: ::::* .: ... :.:.:.:.:.:.:.: :.:.:.:.! 5 ::::,::::::::: :**I :: .*.*.*.*.*.*.*. *.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*. * ........................ ... ..... .6. ............. M .: 0 ... .. .l 9 .01. ..... . .... -:-:-: :-:-:-:-: ........ . ... :::: :::::::: - .. . : --X . -T " ' .:...:.:.:.:.:. .. -:-:-:-:-:-*-* .*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.* .*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.* .. .+ ******* **** .* **** ******* ** ********************** ************************ -- iHHHHHHHHHHH Hiiiiiiiiiiiiiiiiii iiiiiiiiiiiiiiiiii************************** -- HHHHHHHHHH HHHHHHH**** ************************* ********************** ************************ ............................................................................................................................................................................................................... ............................................................................................................................................................................................................... ... ....... ...................... . ....... * :..'.6 ::::: * .... ..... W . ........ :::: .. : ::::::: . .. :::::::: ::::: * :.* *:::: :::::::: ..: ....... ...................... ........................ ... .: .: -* - iiiT :.:.:.:.:.:.:.: i:l .. .............. ............................. ...................... :::::::::I : ..... ... * :::::::: :0 - :: . ::::::: .:*R :: :. . ... :::: :::::*** : : . : . . .................. :.:.:.:.:.: - - :::::::-:-:-:- -- '* D .-.. 7-..:..:..:..::::::::: .*' 9 ..--.. ::::::::::: . *. -- :-:-:-:-:- ::::. i i , * ... ... ... *::::::::::::: :::::::. -* -*.2. : .... *.*.*.*.*.:::: .. .. iii.. i . .. . .................................... . . ::::::: *N. - : a . :::::::::::::::::-:-:- :- :.:.:.:. .:.:.:.:.:.:.:.: : -:, ::::::::::::::::::::::: * * ******************************* ************************* :.:.:.:.:.E .X--.-.-'P : , 2 ::::::::::::::: ** :.......... ... :T ' : 0 3 : : -:-: :-:-:-:-: ...... M 5 1 0 a a .................................................................... .................................. ......... ................ .. ........................ -- - - -- - - -- - - -............ ............................................ ............ - - --- - -- - - - ......................... ...................... ........................ ............................................................................................................................................................................................................... :::::: X p ............ .................... ............................................ ......................... .................. ......................... .................................... .............................................. . 0 :..o .:.............. ................................ .......................... .................... ............................... . .- -. ....... ...................... ........................ .... ....... .. . . ........ ...................... ........................ ** .. ......... ...................... ........................ :: : : : :E ......:J i*.*.& i i i i i i i i * ..... iiii iiiiii*ft ***.:.: -. 3 . ............... ........................ :-'.-4-...7.---*46-:::::::::::::::: " 94::::::: i i i i io.::.q8 .9 : .... : .- : * ::: ::::::D -- :::::::::::::. *** . *:::: ::::::.:.:- :0 .4 :::::::::::i:i:i : : : 2 *'.*...*O *i i i i i i i i i i i i .. ...... ....... :-:-:-: :-:-:-:-:-:-:-.- : ....... ::::::::::::::::::::: ... ... .... :::::::: ::::::::::: ::: .... .... I .. .... ........ . ...... :.:.:.:.:.:.:.: .:.:.:.:.:.:.: ............... ........................ -- - - -- - - -- - - - -- - - -- - - --- ......................... ......................... .................. ......................... ...................... ........................ ............................................................................................................................................................................................................... :::::: X p ............ .................... ............................................ ......................... .................. ......................... ...................... ........................ ....... ., : ...... : :: .. .... X . * ::::: :::::::: .: :::::::: : ** ::: ::::: * .* : -.-.-.-.-.-. .. ............... :.: : ..... j:.j .......... jjjjA :* ... ........ ... .. :*- - .. : -:::: :::::::::I .. ... i............ . .*.*.*.: :-* .. .: . .. .i*. A ... ::::::::: .. : ....... ** ** . .............. ..... ::::il - - - :2 - i i i i i i i i i iD 0 .2 :::::::::::: 1 : '* : :::::::::::::D :: :*I:::::::::::::: 6 : .2 :::::::::::::::.-2 ::.I::. *: * * * * * * . * * ...............- ...... :.:.: * 8 1 ::::::::::::::.:.:.:.:.: : -:,-: .:.:.:.:.:::::::::::::::::.........* ........ ............ :: : : : :E .......:J .*.& i i i i i i i i- -7 6 3 .:.:.:.:.:.:.:. .M 5 .................. 0 - 9 ..... .:.:.:.:.: -:-:-: ..... ................................ .:.:.:.:,.,.,.....,...'a . .................. . .: .............. ................. ... 7r ....... .... ,.,.,., EXP1-7 41.48 1.12 0.30 0.05 1.74 0.04 EXP1-7 46.06 0.75 0.33 0.03 2.08 0.18 EXP1-7 43.10 1.41 0.32 0.02 1.87 0.05 EXP1-7 45.11 1.16 0.30 0.01 1.76 0.12 43.94 2.05 ............................ ..................... ......................... .................. ......................... ...................................... - - - - - -- - --- - - -- - - ............................. ............................................. ............ ............................................ ......................... ...................... ........................ :::::: .... . : ............ ..................... ......................... .................. ......................... ................................................... ............................................ ................................................ .. - :::: .. - .... .... ........ .. .............. ............................................ ......................... . :5 .. ::::::: .. :::: ::::::::::::::G *.. : : .. .... . " " " " ' ...................... -.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-.-. .. 0 ,..Q.. :::::::::::::::::::::::: 4.3 *** :::::::::::::::::::::::: :.,* ........................................................................................................ '2 '.*.. '* ::::::::::::o :. ::::::::::::::::::: -* :::::::::::::::::::::: -- ::::::::O 7-..-: .. .. -- 4 : 0 .*,: -. 4 -'*:::::::::::: G * , * * :: : : :E .... P :l -*-*& i i i i i i i i :::::::::::::::::::::: .- * .** 4 ::::::::::::2. .- * 9.:::: ..: Q ... .......................................................................................... x 5::::::::: 'o 2 ............... .. .. ............... ....................... ......................... ...................... ........................ -- - - -- - - -- - - - -- - - -- - - -- ...... ........ . .... ............................................ ...................... ........................ ................................................................................................................................................................................................................ ..... . * .... ***::::: : .......... * * * :::: :*:*:*:*:*:*:*:* *:.: :. .*.:******* *****.*.*.*.*.*.*.*.*.*.*.*.*.***** *-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-* - . ....... ..... .... ........................ .... ..... .. * .. ........ ..... ... ..... .. ........ ...................... ........................ .. .... ..... .. .. ............... ... ..... ........ ......... ...................... ........... - .:.:.:.:. :.:.:.: . .. .. ........ ..... ... ..... .. ........ ...................... ........................ ..... * -..... ' .- O ... :::: :::::::: * . : . .. .:. - . - . - . - . - . - . - . .. * *6 .:::::::::::::::::::::::::.I::::.7 .*.** 0 6 ............. :.:.:.:.:.: :.:**** . - 4 4 ...... .* :::::::::::::D ::..O .*** . , .... 2 .:::*:::::::: :A : ******* ************************ ************************* i.. . .:.:.:.: .:.:.:.:.:..... .. ...... ...... :.:.:.:.:.E -'.X -'..-'P :..: *'*'8 *.::::::::..:..:..:.*..'.'*... *'.** .1 ::::::::i:i:i:i *,* .... I .......... ::::I.:: .. .::::::::::::: 0 2 8 :i:i:i:if i i i i i i i:.:..;: ........ .... ............................. .................... ................... ......................................................... :- :...:....:.:.:.:.l-:-:-:-:-:-:-:-: ... -..- :...-, -, -, -*- *.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*- *.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.* ********************** ********************* ************* ............ * .............. ........................ ....... ...................... ........................ :**********.*************::**::**::* **** ................ ............................ :.:.: .......... ::::: :......................................................................................................... ................................ ........................ ::::::::: ... : :.. :::: 5 *.**:$. .O : * .... ........................ : * * ::::::: * $. :::::::: :::: ... *... . * * *............... ............................................ ................................................ . . .. .:. ...................... ............................................... :::. ..O : : .** . . -.-. O .. -i ::.A .- T .i.i.i*i*i*i*i i::A * :*********** ::::::::::::::::::::::I:*********************** : ..- - : .. . --::::::::::::O - $ -. ******* ******** :.f :.14 : : : : I: : :I.. .-.. ::: P** .::: .X .p . .... .................. 44 0 ... I ... .. .. .... -:::::::::: ....... 4 :::::::::.:.::::O ".*..** .:..::: : .............. ........ .. :I : : : : : : :& *s : : : : : : : :T :i::: .- * .. .: : : : : : :& .. P : : : : : : :t : -i-: -:-7: :::::::::::::::::::..: -. *-.- ... *.*.*.*.*.*.* -*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-* -*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-*-* -- - - -- - - -- - - ............................... ******iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii**::::: .. ........................................................................................................ ************** ************* . ......................... ...................... ........................ ...... ********************** ********************* ************* ............ .................. ......................... ............................................ ...................... ........................ :**********.*************::**::**::* *** ................. ............................................ ............................................ .......................... ...................... ............................. .............. :.:.:.:.: G .9 - i i i i i i il ;4 i.:.:.:.:.:.:.: .:::::: :::: .. ..... .i::r - --...- :.:.:.:.:.:.:.:::.:.:.:.4 :*. - - ::::::::: ... : :.. :.:.::::** i -2 -. *::::::::::::::::::::::::I::::: - .... ..... :::m .:::::::..:.E .X . -- :-:-:-:-:-:-:-:.:.ii*. .. :::::::::::::::::::::::::::*. ... :::::::::::::::::::::::G .** .iiiiiiIiiiiiiiiiiiiiii : * * ... * * * ............... .- ,.- 5 .. .... . .. R :I::..B ::.*.*.*.*..**..:.4.-...3 .:.--.:.3 ,* -O .:**:::::::::::0 * .2 .- '7 :::::::::::::: M .:.:.:::::::.:.:.:.I .. *........ ................ Q : 0 7 ::: . ... -2 **::::::::::::::::::::: '* .--. '..- ..-.. :::: :::::: *' -2- ::::i*i*E .i.i.A '*.,. -: .6 .. :::::::::::: ............................ ..................... ................... ................... ............................. ...... :.:.:.:.:.:.:.: :.:.:.: ....... ........ :.:.:.: .,.,.,.,., . .- .:::::::::::::: EXP1-9 43.98 0.42 0.27 0.02 1.51 0.06 EXP1-9 , 47.31 1.06 0.35 0.02 1.90 0.19 EXP1-9 44.25 0.96 0.25 0.01 1.52 0.14 EXP1-9 45.03 0.79 0.31 0.04 1.84 0.14 45.14 1 1.51 EXP1 -1 0 37.82 0.38 0.27 0.02 1.29 0.14 EXP1 -1 0 41.16 0.83 0.37 0.06 2.07 0.15 EXP1 -1 0 39.46 0.53 0.41 0.04 2.04 0.12 EXP1 -1 0 41.67 1.30 0.33 1 0.03 1.91 0.21 40.76 1.16 .......................... ..... **************** ************************* ************* ......................... ........................................ -- - - - -- - --- - - -- - - ::*::*::*::************************* *****, **, ********* **********:********:*:*:*:*:*:*:*:************ ......................... .................. ......................... ...................... ........................ :-.-.-.-F -. *..X- .... P : :**** : .... . . .. .: *:::::::::: . ... .......... .................... ..................................... ::::: .. :::::::: :::: ** -- : X . :.:.:.::.:.:.:.:.:.:.: ... ..... ....................... .................. . .. :$ .............. .............................. ...... ... ....................... .... .................... ..................::::::::::: :.............................................. ... . :*::::::::: :::::::: .. -- : ... ........ .... .... .. .:.::::::::::: :**. . :-:iiiiiiii: : : : : : :Z M : : : : : : :4 :::: : 7 : .1 .... ....... .. :*...: : : : :: : : :.a .....*:6 . :1.::::::::::l . . ::::0 4 .. . : .... :.:.:.:.:.:.:.: ........ ........ :: X ... : .. .1.2 . . -a l . * -:-: -:-:-::-:-:-:-:-:-:-:- -X :-. .. :-:-:-:-:..*..*** ************************************* .................. ........ . -:- .T -l *.* *.* : 'D : : :..::. . .:.:.:.:.: . *::::::::::::*i. ... *: .... ....... *********************** .... .... 4 : *.:..:.:.:.:.::::: ... 9 ..... *::::: . 6 .... 6 .: ** 9 0 ............................................ ............................................. ............................. .................... .. ................... .................. ......................... ...................... I ........................ -- - - -- - - -- , - -................... .................. ......................... . ......... ........................ ............................ .............................................................................. :.:.::....... ...***:::: :.*.*.*.*.*.*.*.*.*.*.*.*.*.*.*.* ......... ............................................ .................................. ........................ :************P **:********..**:**..**::**::**: :*:*:*:*****************:* ........... 1. ....... .................. ............................... ............................................ ................................................ ...... ::::::: . ::::: ... ........ .. .............. ............................................ .............................................. ..................................................... :::::::::F- *.-X- -..- :..l:: I *.::::::::::::::::::::. " 3 ....... .................... ....................... .... ....................... .. .................................................... ........................ . .... :::: :::.:.:.l:- .::..3 ::: .i:::B ..- 7 .. ::::::::::::0 .2 ...- ':....... .. :..:..:..:..::: ** 4 ::::::::::::::::::I ::**2 0 *::::*:*:*:':':':':':':':'O :*'O .B .:* ....... ........................ .... : : :::::::: :::.:.- : . .:.:.:.:.::-:-:--:-:-:-: . . ............... ........ ............... ............................................ ................................................ ::::::::::::: . .0 -1 *.*.*.::.:.:.:.:.:.:.:....- .....................................- ......................... .................. ..... ................ - -- - - - - - - -- - -l ............................................ ......................... .................. ......................... ...................... ........................ ................................................................................................................................................................................................................ :::: U . -P * * ***** * *:*** * * * * * * * * * * * * * * ***** *:* * * ******** ***************** *:***** * * * * *:*:*:*:*:*:*:*:* * * * * * * ***** * *:* * * * * * * * * * * * * * * * * *** * * * * * * * * * * * * * *.*.*.*.* * , * * , * * *.*.*.*. * * * * * * * * * * , * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * ................................................ .. :::: ::: . .. . . ........................ ::::: :::: . .:::: .... .... . .... .. ............... ............................................ ................................................ .... ........ .... *:: .: :::::::: .. ....... ........ .:.:.:.: ..... .. * ::::: :::: .. .::::::::::::: :::: . :::: :::::::: .. :::::::: :::: * '* :.. :........ :......i.... .. .. .... ........ ... ........ : .... .: : : * ::::::::******* ******** ***** ** ************************ ** * ................. ............................................ ................................................ ............... . : ::......: .. .N. -:-:-:-::-:-:-:-:-:-:-:-. .N. .. .:.:.:.:.:.:.:.: .:.:.:. .. , . I .- : 0 *:::::::::::: 0 : 2 .- 'I: ........ ...................... ........ .. .T 1 I ........ ....... 3 a l 5 : 1 0 9 0 .:.1 6 ::::::::::::::::::::::G .0 6 ............... C .... .................... ............................................................................................................. ---...................... ................................................................. ......................... .................. ......................... ...................... ........................ ................................................................................................................................................................................................................ :::: .. .. . : .............. ................................................................. ......................... .................. ......................... ...................... ........................ ... .... .... ' :::::.:.:.: i i i io " ... *. ::: .. : ....... ... 2 : ...... . ... . : .. ::::: :::::: . - . . - ..... - ............... .... * * : :A : i*i*A*i*i*i* : I : : : M : : : :I : : : : :.: . .......................... .. . ..:::::: .:.* .. :::: ..... .. :**** :I *.- i*.Q B -l .::::: 4 :::::::::.::.::.::. A. -I . ::::::::::::::::: ............. . . -2 * :::::::::::: .:.:.:.:.:.:.:.:.:.:.:.: . 4 :: .. .. .. ... ...... ....... ...... :::::::::::::** . . .1 G M ,2 :: ***** *:T **T *..*......... ... :::::::::::::::::: . :::2 *** 8 *::::::::::::D :::4 ::::::::::::::.-3 -8 :::2 2 :::::::::::::::::::::::2 ::: : ... .. U PI I ...... 4 .::::::::::::::::::::::::::.I : 1: ............................ .......... ........... ......................... .................. .......... ........................................... X -N ...... :.:.:.:.:.:.:.: -:-:-:-:-...-...- ........... ........................ EXPl-12 1 44.36 1.09 0.41 0.05 2.31 1 0.08 EXPl-12 1 40.13 0.92 0.32 0.06 1.80 0.14 -EXPl-12 1 35.74 , 0.74 , 0.21 0.03 1.04 0.13 , 1 23 WO 2013/122934 PCT/US2013/025744 EXP1-12 40.35 1.99 0.30 0.06 1.81 0.20 40.15 3.52 EXP1-13 47.91 0.45 0.22 0.06 1.67 0.06 EXP1-13 48.20 0.38 0.25 0.04 1.85 0.08 EXP1-13 47.78 0.65 0.26 0.05 1.82 0.11 EXP1-13 46.14 0.65 0.22 0.04 1.43 0.11 47.51 0.93 EXP1-14 44.14 0.59 0.34 0........03 2.04...1 EXP1-14 43.17 1.02 0.33 0,02 1.91 0,1 EXP1-14 40.55 0,88 0.32 DO3 1.79 0,11 EXP1-4 40.89 1.82 034 0G06 1.64 .. 16 42.19 1.75 The data presented in Table 5 and FIG. 1 shows that experiments 2 and 4-9 provide better cleaning than the Commercial Products A-C (shown as experiments 5 10-12) and provide comparable or equal performance to Commercial Products D (shown as experiment 13). These results demonstrate that superior cleaning is achieved in comparison to commercially-available neutral cleaning compositions and at least the same cleaning as non-neutral (alkaline product D) products. 10 EXAMPLE 3 Improved stability of the concentrated formulations of Example 2 was further analyzed. The objective was to evaluate the addition of two different stabilizing agents to concentrate formulation #5 from Example 2 to provide stability 15 (no separation) at high temperatures (50 0 C, oven). Procedure: hydrotropes SXS (96%) and Colatrope INC were added to premade concentrate #5 (from Example 2). Concentrates were agitated until a uniform appearance was achieved and then allowed to equilibrate in a 50 0 C oven for 2 hours. After two hours the samples were removed from the oven and observations 20 of appearance were recorded. Table 6 shows the percentage by wt. of hydrotrope post-added to the concentrated neutral cleaning composition. A passing evaluation was recorded for uniform appearance without separation, cloudy discoloration. A failing evaluation was recorded for any cloudy appearance and/or separation. 25 TABLE 6 24 WO 2013/122934 PCT/US2013/025744 % by wi HIydrotrope Pos Concentrate ID H ydrotrope:~ Ade Pass/Faid Observations 010 SXS (96%) 5% Fail Separation C11 SXS (96%) 6% Fail Separation 012 SXS (96%) 6.25% Fail Separation 013 SXS (96%) 6.50% Fail Separation 014 SXS (96%) 6.75% Fail Separation 015 SXS (96%) 7% Pass Good, uniform appearance 016 SXS (96%) 8% Pass Good, uniform appearance 017 Colatrope INC 5% Fail Separation 018 Colatrope INC 6% Fail Separation 019 Colatrope INC 7% Fail Cloudy 020 Colatrope INC 7.25% Fail Cloudy 021 Colatrope INC 7.50% Fail Cloudy 022 Colatrope INC 7.75% Pass Good, uniform appearance 023 Colatrope INC 8% Pass Good, uniform appearance Table 7 shows the concentrates C10-C23 formulations expressed in % by wt. for the formulations. 5 TABLE 7 Raw Material___ ___ expressed in % by wt. ___ ___ Description 010 C11 C12 C13 C14 C15 C16 Water 77.14% 76.42% 76.24% 76.06% 75.88% 75.70% 75.00% Lutensol XP50 3.81% 3.77% 3.76% 3.76% 3.75% 3.74% 3.70% Pluronic N3 14.29% 14.15% 14.12% 14.08% 14.05% 14.02% 13.89% SXS (96%) 4.76% 5.66% 5.88% 6.10% 6.32% 6.54% 7.41% Colatrope INC 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% Raw Material___ ___ expressed in, % by wt __ Description C17 C18 C1 C20 C21 -C22 C23 Water 77.14% 76.42% 75.70% 75.52% 75.35% 75.17% 75.00% Lutensol XP50 3.81% 3.77% 3.74% 3.73% 3.72% 3.71% 3.70% Pluronic N3 14.29% 14.15% 14.02% 13.99% 13.95% 13.92% 13.89% SXS (96%) 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% Colatrope INC 4.76% 5.66% 6.54% 6.76% 6.98% 7.19% 7.41% 10 The results show that the addition of SXS (96%) at 6.54% by wt and Colatrope INC at 7.19% by wt. provided stability (uniform and clear appearance) when exposed to 50 0 C oven temperatures. A prolonged 4 week oven stability test was later carried out further showing good stability. 15 EXAMPLE 4 The cleaning ability of neutral cleaning compositions according to the invention was evaluated. Formulation C5 (from Example 1) containing hydrotropes 20 added for the purpose of stability was evaluated. Concentrate formulations C15 and 25 WO 2013/122934 PCT/US2013/025744 C23 from Example 3 were further evaluated. Table 8 shows the use solution preparation for the experiment. TABLE 8 5 Exper0mental. Target % by w Tiest ilD Conicentrate ID ilution g Conici g Water NConcentrate EXP3-15 05 0.25 az/gal 0.98 499.05 0.20% EXP3-16 015 0.25 oz/gal 0.98 499.05 0.20% EXP3-17 023 0.25 oz/gal 0.99 499.05 0.20% EXP3-18 Commercial Product A 0.5 az/gal 1.95 498.08 0.39% EXP3-1 9 Commercial Product 0 0.5 az/gal 1 .95 498.03 0.39% The soil application procedure set forth in Example 2 was employed. The cleaning procedure set forth in Example 2 was also employed with one modification 10 - a total of two tiles were tested for EXP3-15. The same data analysis procedure of Example 2 was utilized. The average L value of the 10 soiled coupons was 27.30 with a standard deviation of 0.39. Table 9 and FIG. 2 further show the after clean color data obtained. 26 WO 2013/122934 PCT/US2013/025744 TABLE 9 EXP3-15 49.07 0.67 0.42 0.03 2.57 0.08 49.560 0.693 EXP3-15 50.05 0.79 0.41 0.08 2.51 0.07 EXP3416 46.83 0.82 0.39 0.04 2.15 0.04 EXP3-16~ 46u31 O.86 0.4 O.05 2 09 0.11 EXP3-16~ 47.S4 1.0O1 0.50 O.05 2.92 0.17 EXP3-16~ 4S538 cK95 0.35 O.07 2 04 0.24 EXP3-17 49.02 1.16 0.40 0.05 2.51 0.13 EXP3-17 48.39 1.49 0.35 0.04 2.22 0.06. . EXP3-17 46.60 0.87 0.43 0.03 2.43 0.11 EXP3-17 45.68 1.06 0.36 0.05 2.18 0.07 ____ EXP3-18 37.92 1.34 0.32 0.03 1.61 0.11 EXP3-18 37.36 1.87 0.36 0.06 1.74 0.17 36.970 2.302 EXP3-18 38.94 0.43 0.28 0.84 1.56 0.06 EXP3-18 33.66 0.42 0.33 0.07 1.68 0.07 ___ ____ EXP3-19 50.23 j0.35 V.3S 0.02 j2.28 V.1 EXP3-19 50.47 j0.49 0.3 0.03 2.511 0,1 EXP3-19 50-57 0.42 V.37 O.V43 L2.41 11it EXP3-19 4980 ................ 1 .. 3... Table 9 and FIG. 2 demonstrate experimental conditions 15-17 (Exp3-15, 5 Exp3-16, Exp3-17) according to the neutral cleaning composition of the invention provide efficacious cleaning at a neutral pH. In particular, conditions 16 and 17 had very similar cleaning performance to condition 15. Condition 15 (Exp3-15) had very comparable/equal cleaning performance to condition 19 (Exp3-19, Commercial Product D, daily alkaline cleaner serving as positive control according to the 10 invention). The data further demonstrate the addition of a stabilizing agent provides a formulation with equivalent cleaning performance to current commercial daily alkaline cleaners which has significantly better cleaning performance than current commercial daily neutral cleaners (Exp3-18, condition 18). 15 EXAMPLE 5 Neutral cleaning compositions were further evaluated for formulation modifications to eliminate the need for using glove and goggles when handling the concentrate (e.g. personal protective equipment (PPE)). Formulations having 20 minimized surfactant concentrations to meet regulatory standards (e.g. GHS) for elimination of PPE were evaluated. The cleaning efficacy was evaluated for various formulations containing a reduced level of a water-insoluble Guerbet ethoxylate surfactant. Table 10 shows the various concentrate formulations. Table 11 shows the various use solution preparations. 27 WO 2013/122934 PCT/US2013/025744 TABLE 10 fxpresseci in % by wt Raw Material Description C24 _25_ C26 C27 DI Water 61.94 63.03 61 .94 67.66 Lutensol 3.99 2.90 2.90 2.90 Pluronic 16.96 16.96 18.05 12.33 SXS 16.80 16.80 16.80 16.80 Dye 0.01 0.01 0.01 0.01 Fragranc 0.25 0.25 0.25 0.25 Preservative 0.05 0.05 0.05 0.05 5 TABLE 11 Experimental Target% Test ID Concentrte~ Dilution Cleaner (g) Water (g) Concentrate EXP4-20 024 0.25oz/gal 0.98 499.02 0.20% EXP4-21 025 0.25oz/gal 0.99 499.03 0.20% EXP4-22 026 0.25oz/gal 0.98 499.02 0.20% EXP4-23 027 0.25oz/gal 0.99 499.01 0.20% EXP4-24 Commercial Product A 0.50oz/gal 0.98 249.01 0.39% EXP4-25 Commercial Product D 0.50oz/gal 0.97 249.01 0.39% The soil application procedure set forth in Example 2 was employed. The cleaning procedure set forth in Example 2 was also employed with a modification - a 10 total of two tiles were tested for EXP4-24 and EXP4-25. The same data analysis procedure of Example 2 was utilized. After soiling the coupons, they had very similar color values. One set of five coupons had an L value of 28.24 +/- 0.43 and a second set of five coupons had an L value of 28.10 +/- 0.42. The after clean color data is shown in FIG. 3. 15 Reduction (or elimination) of the PPE requirements of the concentrate formulations of the neutral cleaning compositions of the invention may be achieved as shown in FIG. 3 and this Example 5. Experimental conditions 21 and 22 provide similar cleaning to condition 20 which provides similar cleaning to the commercially-available daily alkaline floor cleaner products (positive control, 20 condition 25). EXAMPLE 6 28 WO 2013/122934 PCT/US2013/025744 The neutral cleaning compositions described according to the invention demonstrate hard surface cleaning efficacy for various conditions and markets. Various concentrations of the formulated neutral cleaning compositions were evaluated. Less concentrated formulations may include those dispensed at 0.5 5 oz/gal and 2.0 oz/gal. A 0.5 oz/gal dispensed formulation was formulated using a one half of a concentrated formulation of Example 5 (0.25 oz/gal dispensed formulation) as shown in Table 12. Additional less concentrated formulations may be employed, including for example a 2.0 oz/gal formulation. 10 TABLE 12 RM Description *obywt. 10003 Water Deionized 80.81 17059 Lutensol XP50 1 .99 17032 Pluronic N3 8.4 17137 SXS 8. 30075 Preservative 0.0 26014 Fragrance 0.2 27120 Dye 0.0 EXAMPLE 7 15 The foam profile of the compositions of the invention was evaluated. In particular, the objective of the trial was to evaluate the foam profile of use solutions of Concentrate 24 in comparison to Commercial Product A. Use Solution Preparation: A 0.25 oz/gal solution was prepared (0.20% solution of concentrate 24) along with a 0.5 oz/gal solution (0.39% solution of 20 Commercial Product A). Foam Test Procedure: 20 mL of each test solution described above (See Use Solution Preparation) was added to a 200 mL graduated cylinder. The graduated cylinders were sealed. An individual held one cylinder in each hand, using the same motion and force, and inverted the cylinders upside down and back 25 to original position for a total of 10 times. Immediately after the 10 inversions, the foam height of each cylinder was recorded according to the mL markings on the cylinders. Again, after 3 minutes the foam height in each cylinder was recorded 29 WO 2013/122934 PCT/US2013/025744 using the mL markings on the cylinders. A higher value (according to the mL markings on the cylinders) indicates more foam generation/presence. Results: Based on this experiment the 0.25 oz/gal use solution of concentrate 24 generated nearly zero foam. Results are shown in Table 13 where the initial level 5 of foam generated by concentrate 24 is less than 1 marking on the cylinder, which is distinct from Commercial Product A generating a significant amount of foam measured by at least 18 markings on the cylinder. After 3 minutes the foam level of concentrate 24 returned to baseline, whereas the foam level of Commercial Product A remained significantly above the baseline. The composition of the present 10 invention demonstrates clear benefits of providing a low-foam or no-foam profile. TABLE 13 I solution level 20I 20 Afterf10Ihive rsions 3E <21 Afte r 3 min utes 26 20 15 The inventions being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the inventions and all such modifications are intended to be included within the scope of the following claims. 20 30
权利要求:
Claims (20) [1] 1. A concentrated neutral floor treatment composition comprising: about 1-50 wt-% of at least two water-insoluble surfactants, wherein a first 5 surfactant is a branched alcohol alkoxylate and a second surfactant is an ethylene oxide/propylene oxide copolymer; and about 1-50 wt-% of a water-soluble anionic hydrotrope; and about 20-90 wt-% water, wherein the composition has a pH from about 6 to 9 and 10 forms a clear solution. [2] 2. The composition according to claim 1 wherein the branched alcohol alkoxylate is a Guerbet ethoxylate having the formula 15 CH 3 (CH 2 )nCHCH 2 O(CH 2 CHO)mH I I R IR 2 wherein R 1 is a C2-C20 alkyl, R 2 is a H or C1-C4 alkyl, n is 2-20, and m is 1-40. 20 [3] 3. The composition according to claim 1 wherein the EO-PO copolymer is selected from the group consisting of a EO-PO copolymer, a reverse EO-PO copolymer and combinations thereof. 25 [4] 4. The composition according to claim 2 wherein the water-insoluble Guerbet ethoxylate is about 30 wt-% to about 60 wt-% ethylene oxide, wherein the ethylene oxide/propylene oxide copolymer is a reverse copolymer, and wherein the anionic hydrotrope is selected from the group consisting of xylene sulfonate and its salts, cumene sulfonate and its salts, and a C6-C1O fatty acid and its salts. 30 [5] 5. The composition of claim 1, wherein the weight ratios of said second surfactant to said first surfactant to said hydrotrope are from about 20:1:20 to about 2:1:2. 31 WO 2013/122934 PCT/US2013/025744 [6] 6. A concentrated neutral floor treatment composition comprising: about 1-10 wt-% of a water-insoluble Guerbet ethoxylate having the following formula; 5 CH 3 (CH 2 )nCHCH 2 O(CH 2 CHO)mH I I R IR 2 10 about 1-50 wt-% of a water-insoluble EO-PO copolymer; about 1-50 wt-% of a water-soluble anionic hydrotrope; and about 20-90 wt-% water, wherein the composition has a pH from about 6 to 9 and forms a clear solution. 15 [7] 7. The composition according to claim 6 wherein R is a C2-C20 alkyl, R2 is a H or C1-C4 alkyl, n is 2-20, and m is 1-40, and wherein the Guerbet ethoxylate is prepared from a Guerbet alcohol by dimerization of an alkene. [8] 8 The composition according to claim 6 wherein the water-insoluble Guerbet 20 ethoxylate is about 30 wt-% to about 60 wt-% ethylene oxide, and wherein the EO PO copolymer has a molecular weight less than about 10,000 and is selected from the group consisting of a EO-PO copolymer, a reverse EO-PO copolymer and combinations thereof. 25 [9] 9. The composition according to claim 6 wherein the compositions retains phase stability at elevated temperatures of up to about 50'C. [10] 10. The composition according to claim 6 wherein the water-insoluble Guerbet ethoxylate is about 30 wt-% to about 60 wt-% ethylene oxide, wherein the ethylene 30 oxide/propylene oxide copolymer is a reverse copolymer, and wherein the anionic hydrotrope is selected from the group consisting of xylene sulfonate and its salts, cumene sulfonate and its salts, and a C6-C1O fatty acid and its salts. 32 WO 2013/122934 PCT/US2013/025744 [11] 11. The composition according to claim 6 wherein the weight ratio of EO-PO copolymer surfactant to water-insoluble Guerbet ethoxylate surfactant to anionic hydrotrope is from about 20:1:20 to about 2:1:2. 5 [12] 12. The composition according to claim 6 wherein the composition does not contain any agents selected from the group consisting of a builder, chelant, sequestrant, threshold agent/inhibitor and combinations thereof. [13] 13. The composition according to claim 6 wherein the composition does not 10 include a viscosity modifier and/or organic solvent. [14] 14. A kit comprising: a liquid detergent composition, wherein said composition is the neutral cleaning composition 15 according to claim 6; a container; and instructions for use of the kit. [15] 15. The kit of claim 14 and further comprising a removal agent for use in 20 applying the neutral cleaning compositions and removing a plurality of soils. [16] 16. A method for cleaning a hard surface comprising: applying to the hard surface a neutral cleaning composition comprising about 1-10 wt-% a 25 water-insoluble Guerbet ethoxylate surfactant having the following formula CH 3 (CH 2 )nCHCH 2 O(CH 2 CHO)mH I I R IR 2 30 about 1-50 wt-% of a water-insoluble EO-PO copolymer surfactant, about 1 50 wt-% of a water-soluble anionic hydrotrope and about 20-90 wt-% of 33 WO 2013/122934 PCT/US2013/025744 water, wherein the composition has a pH from about 6 to 9 and forms a clear solution. [17] 17. The method according to claim 16 further comprising a step of diluting the 5 composition into a use solution with water before applying the composition to a hard surface, and wherein the dilution provides a dispensing rate of a use solution of the neutral cleaning composition from about 0.1 oz./gal to about 10 oz./gal. [18] 18. The method according to claim 16 wherein the neutral cleaning composition 10 provides at least equivalent cleaning efficacy in comparison to alkaline cleaning solutions. [19] 19. The method according to claim 16 wherein the neutral cleaning composition does not require use of personal protective equipment by an end-user. 15 [20] 20. The method of claim 16 further comprising removing soil from the hard surface using a removal agent selected from the group consisting of a mop, auto scrubber, spray dispenser, compressed air and combinations thereof. 20 34
类似技术:
公开号 | 公开日 | 专利标题 AU2013221822B2|2016-02-25|Neutral floor cleaner AU668201B2|1996-04-26|Thickened acid microemulsion composition AU720211B2|2000-05-25|Alkaline aqueous hard surface cleaning compositions EP1945745B1|2011-07-20|Acidic cleaning compositions US20100029534A1|2010-02-04|Cleaning Compositions and Methods NZ234513A|1997-03-24|Acidic aqueous hard surface cleaner comprising organic detergent, c| organic acids |, aminoalkylenephosphonic acid and phosphoric acid for use on acid resistant hard surfaces and zirconium white enamel WO2012080884A2|2012-06-21|Soil resistant floor treatment JP2005154716A|2005-06-16|Detergent composition for automatic dishwashers JP2006008801A|2006-01-12|Detergent composition for hard surface TWI223662B|2004-11-11|Liquid detergent JP5336160B2|2013-11-06|Antibacterial composition CN110272783B|2021-03-26|Multifunctional cleaning agent and preparation method thereof NZ260608A|1995-02-24|Micro-emulsion cleansers comprising an organic detergent, an alpha-oh aliphatic acid, and aminoalkylene phosphonic acid WO2016055264A1|2016-04-14|Liquid hard surface cleaning composition BR112020017802A2|2020-12-22|WATER CLEANING FORMULATION JPH0820794A|1996-01-23|Detergent composition for hard surface GB2527347A|2015-12-23|Cleaning formulation
同族专利:
公开号 | 公开日 EP3345988A1|2018-07-11| CN104334703A|2015-02-04| BR112014016115A2|2017-06-13| EP2814926A1|2014-12-24| EP3138894A1|2017-03-08| BR112014016115B1|2021-09-08| EP3345988B1|2020-06-17| CN104334703B|2018-02-27| EP3138894B1|2018-03-28| EP2814926B1|2016-12-14| AU2013221822B2|2016-02-25| US20150210958A1|2015-07-30| US9512384B2|2016-12-06| ES2827803T3|2021-05-24| ES2675780T3|2018-07-12| BR112014016115A8|2017-07-04| ES2616806T3|2017-06-14| WO2013122934A1|2013-08-22| JP6126136B2|2017-05-10| US20130213435A1|2013-08-22| JP2015512970A|2015-04-30| EP2814926A4|2015-10-21| US9029309B2|2015-05-12|
引用文献:
公开号 | 申请日 | 公开日 | 申请人 | 专利标题 US3048548A|1959-05-26|1962-08-07|Economics Lab|Defoaming detergent composition| BE624833A|1962-02-28|||| US3442242A|1967-06-05|1969-05-06|Algonquin Shipping & Trading|Stopping and manoeuvering means for large vessels| DE2243307C2|1972-09-02|1982-04-15|Henkel KGaA, 4000 Düsseldorf|Solid detergents and washing auxiliaries with a content of anti-graying additives| DE2301728C2|1973-01-13|1982-09-02|Henkel KGaA, 4000 Düsseldorf|Liquid laundry detergent and auxiliary agent with a content of anti-graying additives| DE2916656A1|1979-04-25|1980-11-06|Henkel Kgaa|Optical brightener-free textile detergent compsn. - contg. aliphatic polyglycol ether, alkyl-pyridinium salt and standard additives| JPH0768555B2|1986-12-13|1995-07-26|ライオン株式会社|Detergent composition for automatic dishwasher| US5468423A|1992-02-07|1995-11-21|The Clorox Company|Reduced residue hard surface cleaner| BR9306243A|1992-04-13|1998-06-23|Procter & Gamble|Composition for automatic washing of thixotropic liquid dishes with enzyme| US5382376A|1992-10-02|1995-01-17|The Procter & Gamble Company|Hard surface detergent compositions| US5415814A|1993-08-27|1995-05-16|The Procter & Gamble Company|Concentrated liquid or gel light duty dishwashing detergent composition containing calcium xylene sulfonate| EP0709450A1|1994-10-24|1996-05-01|The Procter & Gamble Company|Low sudsing liquid detergent compositions| MX9704500A|1994-12-16|1997-10-31|Procter & Gamble|Hard surface cleaners comprising highly ethoxylated guerbet alcohols.| GB9703054D0|1997-02-14|1997-04-02|Ici Plc|Agrochemical surfactant compositions| US5871590A|1997-02-25|1999-02-16|Ecolab Inc.|Vehicle cleaning and drying compositions| EP0878535B1|1997-05-16|2003-04-16|The Procter & Gamble Company|Light-duty liquid or gel dishwashing detergent compositions which are microemulsions and which have desirable greasy food soil removal and sudsing characteristics.| US5977048A|1997-07-29|1999-11-02|Basf Corporation|Aqueous based solvent free cleaning degreaser compositions containing alcohol alkoxylates, polyoxyalkylene block copolymers, and fatty alcohols having oxyethylate moieties| CN1281500A|1997-10-14|2001-01-24|普罗格特-甘布尔公司|Light-duty liquid or gel dishwashing detergent compositions comprising mid-chain branched surfactants| US6387856B1|1998-09-25|2002-05-14|Procter & Gamble Company|Antimicrobial detergent compositions containing iodine ions| DE19859911A1|1998-12-23|2000-06-29|Basf Ag|Process for the preparation of surfactant alcohols and surfactant alcohol ethers, the products produced and their use| CN1378585A|1999-01-20|2002-11-06|宝洁公司|Dish washing compositions comprising modified alkylbenzene sulfonates| DE19912418A1|1999-03-19|2000-09-21|Basf Ag|Process for the preparation of surfactant alcohols and surfactant alcohol ethers, the products produced and their use| US6180592B1|1999-03-24|2001-01-30|Ecolab Inc.|Hydrophobic and particulate soil removal composition and method for removal of hydrophobic and particulate soil| US6387870B1|1999-03-29|2002-05-14|Ecolab Inc.|Solid pot and pan detergent| US6369021B1|1999-05-07|2002-04-09|Ecolab Inc.|Detergent composition and method for removing soil| US6425959B1|1999-06-24|2002-07-30|Ecolab Inc.|Detergent compositions for the removal of complex organic or greasy soils| US6716805B1|1999-09-27|2004-04-06|The Procter & Gamble Company|Hard surface cleaning compositions, premoistened wipes, methods of use, and articles comprising said compositions or wipes and instructions for use resulting in easier cleaning and maintenance, improved surface appearance and/or hygiene under stress conditions such as no-rinse| DE10003567A1|2000-01-27|2001-08-09|Henkel Kgaa|Combination of surfactants| US6673760B1|2000-06-29|2004-01-06|Ecolab Inc.|Rinse agent composition and method for rinsing a substrate surface| US6362149B1|2000-08-03|2002-03-26|Ecolab Inc.|Plastics compatible detergent composition and method of cleaning plastics comprising reverse polyoxyalkylene block co-polymer| US6462014B1|2001-04-09|2002-10-08|Akzo Nobel N.V.|Low foaming/defoaming compositions containing alkoxylated quaternary ammonium compounds| US6786223B2|2001-10-11|2004-09-07|S. C. Johnson & Son, Inc.|Hard surface cleaners which provide improved fragrance retention properties to hard surfaces| US6881711B1|2001-10-26|2005-04-19|Prestone Products Corporation|Low VOC cleaning compositions for hard surfaces| CA2521034A1|2003-04-02|2004-10-21|Merck & Co., Inc.|Mass spectrometry data analysis techniques| SE526170C2|2003-05-07|2005-07-19|Akzo Nobel Nv|Aqueous composition containing an alkylene oxide adduct, a hexyl glucoside and an active nonionic alkylene oxide adduct as a wetting agent| GB2408512A|2003-11-26|2005-06-01|Reckitt Benckiser Inc|Floor treatment compositions comprising an amphoteric hydrotrope| JP2008507611A|2004-07-23|2008-03-13|ザプロクターアンドギャンブルカンパニー|Liquid detergent composition that improves detergency at low temperatures against oil and starch stains| JP2006124627A|2004-09-29|2006-05-18|Daisan Kogyo Kk|Cip agent composition and cleaning agent composition for manufacturing apparatus of food and drink, and method of using the same| JP2008516047A|2004-10-04|2008-05-15|ザプロクターアンドギャンブルカンパニー|Composition containing metal complex dye and surfactant| JP2008520766A|2004-11-15|2008-06-19|ザプロクターアンドギャンブルカンパニー|Liquid detergent composition for improved low temperature oil cleaning| JP2006335896A|2005-06-02|2006-12-14|Daisan Kogyo Kk|Cleaning agent composition for container and cleaning method using the same| JP2007077290A|2005-09-14|2007-03-29|Daisan Kogyo Kk|Deodorant composition for cip| AU2006320852B2|2005-11-30|2012-03-08|Ecolab Inc.|Detergent composition containing branched alcohol alkoxylate and compatibilizing surfactant, and method for using| AU2006330669A1|2005-12-20|2007-07-05|Novozymes Biologicals, Inc.|Surfactants systems for surface cleaning| JP5079290B2|2006-09-21|2012-11-21|ディバーシー株式会社|Antifouling detergent composition for bathrooms, cleaning composition impregnated with the composition, and cleaning method using them| JP5179168B2|2007-12-28|2013-04-10|花王株式会社|Liquid detergent composition for dishwashers| US8246696B2|2010-09-17|2012-08-21|Ecolab Usa Inc.|Cleaning compositions employing extended chain anionic surfactants| US9029309B2|2012-02-17|2015-05-12|Ecolab Usa Inc.|Neutral floor cleaner|US5282156A|1991-01-31|1994-01-25|Matsushita Electric Industrial Co., Ltd.|Leading one anticipator and floating point addition/subtraction apparatus employing same| US9029309B2|2012-02-17|2015-05-12|Ecolab Usa Inc.|Neutral floor cleaner| US20140004194A1|2012-05-21|2014-01-02|University Of Maryland|Highly stable colloid from aqueous solutions of small organic molecules| JP6961605B2|2016-03-04|2021-11-05|エス.シー. ジョンソン アンド サン、インコーポレイテッド|Multipurpose floor finishing composition| US11046913B2|2016-03-04|2021-06-29|S. C. Johnson & Son, Inc.|Neutral floor cleaner compositions| WO2021055159A1|2019-09-16|2021-03-25|Colgate-Palmolive Company|Home care compositions| CN111454784A|2020-04-30|2020-07-28|中山榄菊日化实业有限公司|Floor cleaning agent and preparation method thereof|
法律状态:
2016-06-23| FGA| Letters patent sealed or granted (standard patent)| 2018-07-19| DA3| Amendments made section 104|Free format text: THE NATURE OF THE AMENDMENT IS: AMEND THE NAME OF THE INVENTOR TO READ HANSON, CATHERINE; WOLD, ANDREW; GIOINO, TRACI; SMITH, KIM R. AND KILLEEN, YVONNE MARIE |
优先权:
[返回顶部]
申请号 | 申请日 | 专利标题 US13/399,130|US9029309B2|2012-02-17|2012-02-17|Neutral floor cleaner| US13/399,130||2012-02-17|| PCT/US2013/025744|WO2013122934A1|2012-02-17|2013-02-12|Neutral floor cleaner| 相关专利
Sulfonates, polymers, resist compositions and patterning process
Washing machine
Washing machine
Device for fixture finishing and tension adjusting of membrane
Structure for Equipping Band in a Plane Cathode Ray Tube
Process for preparation of 7 alpha-carboxyl 9, 11-epoxy steroids and intermediates useful therein an
国家/地区
|