Water-based hard surface cleaning formulations

Abstract

1. An aqueous hard surface cleaning formulation comprising: water, 0.1 to <5 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of a non-ionic branched alcohol alkoxylate surfactant having a hydrophobic-lipophilic balance (HLB) of 0.5 to 11.5, and 0.01 wt. % to 25 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of a compound of formula (I): [Formula 1] JPEG2025507618000020.jpg16170 (wherein T is on average >2.5 to 14) and an ethoxylated phenol having the formula: wherein the weight ratio of the weight of the ethoxylated phenol contained in the aqueous hard surface cleaning formulation divided by the weight of the nonionic branched alcohol alkoxylate surfactant is 0.1 to <5.

Description

[Technical field]

[0001] The present invention relates to an aqueous hard surface cleaning formulation. In particular, the present invention relates to an aqueous hard surface cleaning formulation comprising: (a) water; (b) 0.1 to <5 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of a nonionic branched alcohol alkoxylate surfactant having a hydrophobic-lipophilic balance (HLB) of 0.5 to 11.5; and (c) 0.01 wt. % to 25 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of a compound of formula (I): [ka] (wherein T is on average >2.5 to 14) and an ethoxylated phenol having the formula: wherein the weight ratio of the weight of the ethoxylated phenol (c) contained in the aqueous hard surface cleaning formulation divided by the weight of the nonionic surfactant (b) is 0.1 to <5.

[0002] Aqueous hard surface cleaning compositions have a wide range of uses, such as for cleaning hard surfaces such as floors, counters, walls, tables, and other objects made of, for example, wood, stone, laminate, ceramic, and plastic materials that require periodic cleaning of built-up dirt, oil, grease, and other contaminants.

[0003] Low hydrophilic-lipophilic balance (HLB) nonionic surfactants are recognized as useful components for aqueous hard surface cleaning compositions, considering that they facilitate the removal of greasy soil from hard surfaces.However, such low HLB nonionic surfactants tend to be insoluble in water-rich formulations.Therefore, the incorporation of low HLB surfactants into aqueous hard surface cleaning compositions can lead to concerns about the instability of the formulation, which manifests itself by phase separation in the composition container, resulting in undesirable product appearance and inconsistent delivery of surfactant to hard surfaces for cleaning.

[0004] To facilitate the formulation of low HLB nonionic surfactants into aqueous hard surface cleaning compositions, a conventional approach is to blend a high HLB surfactant or an ionic surfactant (e.g., an anionic surfactant) with the low HLB nonionic surfactant to facilitate solubilization of the low HLB nonionic surfactant in the formulation.

[0005] Nevertheless, there continues to be a need for effective aqueous hard surface cleaning formulations that do not require the inclusion of high HLB or ionic surfactants to stabilize the formulation from phase separation.

[0006] The present invention relates to an aqueous hard surface cleaning formulation comprising: (a) water; (b) 0.1 to <5 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of a nonionic branched alcohol alkoxylate surfactant having a hydrophobic-lipophilic balance (HLB) of 0.5 to 11.5; and (c) 0.01 wt. % to 25 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of a compound of formula (I): [ka] (wherein T is on average >2.5 to 14) and an ethoxylated phenol having the formula: wherein the weight ratio of the weight of the ethoxylated phenol (c) contained in the aqueous hard surface cleaning formulation divided by the weight of the nonionic surfactant (b) is 0.1 to <5, and the aqueous hard surface cleaning formulation contains less than 0.003 wt.% of at least one C based on the weight of the aqueous hard surface cleaning formulation. 8~18a quaternary ammonium salt having an alkyl group, the aqueous hard surface cleaning formulation containing less than 0.05% by weight of the aqueous hard surface cleaning formulation of a cationic biocide, the cationic biocide being selected from the group consisting of quaternary ammonium salts ("quats") and biguanide compounds, the aqueous hard surface cleaning formulation containing <0.01% by weight of the aqueous hard surface cleaning formulation of a castor oil derivative, the aqueous hard surface cleaning formulation containing <0.5% by weight of the aqueous hard surface cleaning formulation or % by weight of a mixture of (i) an aminocarboxylic acid chelator and (ii) a polycarboxylic acid chelator, wherein the aminocarboxylic acid chelator is a chelating agent having a nitrogen atom and a carboxy group, and the polycarboxylic acid chelator is a chelating agent having at least two functional groups per molecule including at least one carboxy group, the functional groups being selected from carboxy groups and hydroxy groups; and the aqueous hard surface cleaning formulation comprises less than 0.5 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of a compound of formula (VI): [ka] (wherein p is 1 or 2). The present invention provides an aqueous hard surface cleaning formulation comprising the components:

[0007] The present invention provides a method of cleaning a hard surface comprising selecting an aqueous hard surface cleaning formulation of the present invention, applying the aqueous hard surface cleaning formulation to a soiled hard surface having material to be removed, and scrubbing the aqueous hard surface cleaning formulation onto the soiled hard surface to provide a cleaned hard surface, wherein at least some of the material to be removed has been removed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Applicants have surprisingly discovered that a polymerizable composition comprising (b) a nonionic branched alcohol alkoxylate surfactant having a hydrophobic-lipophilic balance (HLB) of 0.5 to 11.5 and (c) a polymerizable compound having the formula (I): [ka] (wherein T is on average >2.5 to 14) and an ethoxylated phenol having the formula (c) and a weight ratio of (b) of from 0.1 to <5, provide a formulation that exhibits a cloud point temperature of from 25 to <40°C, and that exhibits exceptional cleaning performance against greasy soils while at the same time being phase stable after storage for 20 days at 21°C.

[0009] Unless otherwise indicated, ratios, percentages, parts, etc. are by weight. Weight percentages (or wt %) in a composition are percentages of dry weight, i.e., excluding any water that may be present in the composition. Percentages of monomer units in a polymer are percentages of solids weight, i.e., excluding any water present in a polymer emulsion.

[0010] As used herein, unless otherwise indicated, the terms "weight average molecular weight" and "Mw" are used interchangeably to refer to weight average molecular weight measured in the conventional manner using gel permeation chromatography (GPC) and conventional standards such as polyethylene glycol standards. The technique of GPC is discussed in detail in Modem Size Exclusion Chromatography, WW Yau, JJ Kirkland, DDBly; Wiley-Interscience, 1979, and A Guide to Materials Characterization and Chemical Analysis, JP Sibilia; VCH, 1988, p.81-84. Weight average molecular weight is reported herein in units of Daltons.

[0011] The term "hard surface" as used herein and in the appended claims means any porous or non-porous inanimate surface. Preferred hard surfaces are selected from the group consisting of ceramic (e.g., toilets, sinks, showers, kitchen and bath tiles), glass (e.g., windows), metal (e.g., drains, faucets, fixtures), polymers (e.g., PVC plumbing, fiberglass, Corian®), stone (e.g., granite, marble), and combinations thereof, and the hard surface is not a silicon wafer or semiconductor substrate.

[0012] The term "hydrophile-lipophile balance" or "HLB" as used in this specification and the appended claims refers to the HLB value calculated by the effective chain length (ECL) method using the formulas (Formula 1) to (Formula 3) (X. Guo et al., Calculation of hydrophile-lipophile balance for polyethoxylated surfactants by group contribution method, Journal of Colloid and Interface Science 298 (2006) 441-450).

number

[0013] Preferably, the aqueous hard surface cleaning formulations of the present invention are selected from the group consisting of aqueous multi-surface cleansers, floor cleansers, kitchen cleansers, bathroom cleansers. More preferably, the aqueous hard surface cleaning formulations of the present invention are selected from the group consisting of floor cleansers and kitchen cleansers.

[0014] Preferably, the aqueous hard surface cleaning formulation of the present invention comprises (a) water (preferably 10 to 99.99 wt % (more preferably 25 to 98 wt %, most preferably 50 to 97 wt %) of water, based on the weight of the aqueous cleaning formulation); (b) 0.1 to <5 wt % (preferably 0.25 to 4 wt %, more preferably 0.5 wt % to 3.5 wt %, most preferably 0.75 to 3 wt %) of a nonionic branched alcohol alkoxylate surfactant having a hydrophobic-lipophilic balance (HLB) of 0.5 to 11.5 (preferably 3 to 11, more preferably 6 to <11, most preferably 7 to 10.75), based on the weight of the aqueous hard surface cleaning formulation; and (c) 0.01 wt % to 25 wt % (preferably 0.1 to 20 wt %, more preferably 0.5 wt % to 15 wt %, most preferably 1 to 10 wt %) of a compound of formula (I): [ka] (In the formula, T is an average of >2.5 to 14 (preferably 3 to 10, more preferably 3.25 to 8, even more preferably 3.5 to 7, and most preferably 3.75 to 6.5). and an ethoxylated phenol having the formula (c) / (b), which is equal to the weight of the ethoxylated phenol (c) contained in the aqueous hard surface cleaning formulation divided by the weight of the nonionic surfactant (b) contained in the aqueous hard surface cleaning formulation, is 0.1 to <5, and the weight ratio of the ethoxylated phenol (c) contained in the aqueous hard surface cleaning formulation divided by the weight of the nonionic surfactant (b) is 0.1 to <5 (preferably, 0.1 to 4.75, more preferably, 1 to 4.5, and most preferably, 1.5 to 4.25), and the aqueous hard surface cleaning formulation contains less than 0.003 wt. % (preferably, <0.001 wt. %, more preferably, <0.0001 wt. %, and most preferably, below the detection limit) of at least one C based on the weight of the aqueous hard surface cleaning formulation. 8~18and wherein the aqueous hard surface cleaning formulation contains less than 0.05 wt. % (preferably, <0.01 wt. %, more preferably, less than 0.001 wt. %, even more preferably, <0.0001 wt. %, and most preferably, below the detection limit) of a cationic biocide based on the weight of the aqueous hard surface cleaning formulation, the cationic biocide being selected from the group consisting of quaternary ammonium salts ("quats") and biguanide compounds; and wherein the aqueous hard surface cleaning formulation contains less than 0.05 wt. % (preferably, <0.01 wt. %, more preferably, less than 0.001 wt. %, even more preferably, <0.0001 wt. %, and most preferably, below the detection limit) of a cationic biocide based on the weight of the aqueous hard surface cleaning formulation, the cationic biocide being selected from the group consisting of quaternary ammonium salts ("quats") and biguanide compounds. The cleaning formulation contains <0.01 wt. % (preferably <0.001 wt. %, more preferably <0.0001 wt. %, most preferably <detection limit) of a castor oil derivative based on the weight of the aqueous hard surface cleaning formulation, and the aqueous hard surface cleaning formulation contains <0.5 wt. % or >3 wt. % (preferably <0.1 wt. % or >5 wt. %, more preferably <0.01 wt. %, even more preferably <0.001 wt. %, most preferably <detection limit) of a castor oil derivative based on the weight of the aqueous hard surface cleaning formulation. The aqueous hard surface cleaning formulation comprises a mixture of (a) an aminocarboxylic acid chelator and (b) a polycarboxylic acid chelator, the aminocarboxylic acid chelator being a chelating agent having a nitrogen atom and a carboxy group, the polycarboxylic acid chelator being a chelating agent having at least two functional groups per molecule including at least one carboxy group, the functional groups being selected from carboxy and hydroxy groups (e.g., acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, gluconic acid, and salts thereof), the aqueous hard surface cleaning formulation comprising less than 0.5 wt. % (preferably, <0.1 wt. %, more preferably, <0.01 wt. %, even more preferably, <0.001 wt. %, and most preferably, below the detectable limit) of a carboxylic acid represented by formula (VI): [ka] (wherein p is 1 or 2 (or p is 1 to 8)) Contains the ingredients:

[0015] Preferably, the aqueous hard surface cleaning formulation of the present invention comprises (a) 10 to 99.99% by weight (preferably, 25 to 98% by weight, more preferably, 50 to 97% by weight) of water based on the weight of the aqueous hard surface cleaning formulation. Preferably, the aqueous hard surface cleaning formulation of the present invention comprises (a) 10 to 99.99% by weight (preferably, 25 to 98% by weight, most preferably, 50 to 97% by weight) of water based on the weight of the aqueous hard surface cleaning formulation, and the water is at least one of distilled water, deionized water, and industrial soft water.

[0016] Preferably, the aqueous hard surface cleaning formulation of the present invention comprises (b) 0.1 to <5 wt. % (preferably 0.25 to 4 wt. %, more preferably 0.5 to 3.5 wt. %, and most preferably 0.75 to 3 wt. %) of a nonionic branched alcohol alkoxylate surfactant having a hydrophobic-lipophilic balance (HLB) of 0.5 to 11.5 (preferably 3 to 11, more preferably 6 to <11, and most preferably 7 to 10.75), based on the weight of the aqueous hard surface cleaning formulation. More preferably, the aqueous hard surface cleaning formulation of the present invention comprises (b) 0.1 to <5 wt. % (more preferably 0.25 to 4 wt. %, more preferably 0.5 wt. % to 3.5 wt. %, and most preferably 0.75 to 3 wt. %) of a nonionic branched alcohol alkoxylate surfactant having a hydrophobic-lipophilic balance (HLB) of 0.5 to 11.5 (preferably 3 to 11, more preferably 6 to <11, and most preferably 7 to 10.75), based on the weight of the aqueous hard surface cleaning formulation, the nonionic branched alcohol alkoxylate surfactant having a hydrophobic-lipophilic balance (HLB) of 0.5 to 11.5 (preferably 3 to 11, more preferably 6 to <11, and most preferably 7 to 10.75), the nonionic branched alcohol alkoxylate surfactant having formula (II): [ka] (In the formula, w is an average of 4 to 20 (preferably 4 to 15, more preferably 4 to 12, and most preferably 4 to 10), and R 1 is hydrogen and linear or branched C 1~20 Alkyl groups (preferably hydrogen and linear or branched C 1~15Alkyl groups, more preferably hydrogen and linear C 1-15 alkyl groups), R 2 is a branched C 1~20 Alkyl groups and linear or branched C 1~4 Hydroxyalkyl groups (preferably branched C 1~15 Alkyl groups and linear or branched C 1~4 Hydroxyalkyl groups, more preferably C 1~15 Alkyl groups and linear or branched C 1~3 Hydroxyalkyl groups, most preferably linear C 1~15 alkyl groups), each R 3 are independently selected from the group consisting of hydrogen, a methyl group, and an ethyl group (preferably, all R 3 is hydrogen or R in the surfactant molecule 3 Some of the R in the surfactant molecule are hydrogen. 3 some of which are methyl groups), R 1 and R 2 The total number of carbon atoms in the formula (I) is 5 to 21 (preferably 6 to 20 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 7 to 15 carbon atoms). It is a surfactant having the formula:

[0017] Preferably, the aqueous hard surface cleaning formulation of the present invention comprises (c) 0.01% to 25% by weight (more preferably 0.1 to 20% by weight, more preferably 0.5% to 15% by weight, most preferably 1 to 10% by weight) of a compound of formula (I): [ka] (In the formula, T is an average of >2.5 to 14 (preferably 3 to 10, more preferably 3.25 to 8, even more preferably 3.5 to 7, and most preferably 3.75 to 6.5). The ethoxylated phenols include those having the formula:

[0018] Preferably, the aqueous hard surface cleaning formulation of the present invention has a weight ratio (c) / (b) of ethoxylated phenol (c) to nonionic surfactant (b), which is equal to the weight of the ethoxylated phenol (c) contained in the aqueous hard surface cleaning formulation divided by the weight of the nonionic surfactant (b) contained in the aqueous hard surface cleaning formulation, of 0.1 to <5 (preferably, 0.1 to 4.75, more preferably, 1 to 4.5, and most preferably, 1.5 to 4.25).

[0019] Preferably, the aqueous hard surface cleaning formulation has a cleaning performance of at least 50% (preferably, at least 60%, more preferably, at least 65%, and most preferably, at least 70%). More preferably, the aqueous hard surface cleaning formulation has a cleaning performance of at least 50% (preferably at least 60%, more preferably at least 65%, and most preferably at least 70%), which cleaning performance is measured when the aqueous hard surface cleaning formulation is applied to a tile (e.g., Premium Excelon Feature Tile & Strip, Chalk II 56830 / L597A available from ArmstrongFlooring) soiled with a mixture of 61.04% by weight naphtha 60 / 110, 27.6% by weight Cognis Myritol 318, 8.2% by weight soybean oil, and 3.18% by weight carbon black (Mogul L) and scrubbed with a carpeted scrubber (i.e., The Felt Store Inc. (West The gray value is determined by scrubbing a wet surface for 5 minutes using 3 mm needle punch carpet (purchased from San Jose, Seneca, NY) to provide a cleaned tile and comparing the gray value of the cleaned tile to the gray values ​​of an unused tile (100% cleaned) and a soiled tile before cleaning (0% cleaned). Most preferably, the aqueous hard surface cleaning formulation has a cleaning performance of at least 50% (preferably at least 60%, more preferably at least 65%, and most preferably at least 70%), the cleaning performance being determined as described in the Examples.

[0020] Preferably, the aqueous hard surface cleaning formulations of the present invention are phase stable after storage for 20 days at 21° C. Preferably, the aqueous hard surface cleaning formulations of the present invention are phase stable after storage for 20 days at 21° C., and the aqueous hard surface cleaning formulations are determined to be phase stable by placing 100 mL of the formulation in a glass container and observing for the presence of a phase partitioned into two or more layers after storage for 20 days at 21° C. The aqueous hard surface cleaning formulation is determined to be phase stable if, after the storage period, (i) only one layer is observed in the glass container, or (ii) if partitioning is observed, there is a major layer in the glass container comprising at least 90% by weight (preferably at least 95% by weight, more preferably at least 97.5% by weight, and most preferably at least 98% by weight) of the aqueous hard surface cleaning formulation.

[0021] Preferably, the aqueous hard surface cleaning formulation of the present invention has a cloud point temperature of 25°C to <40°C (preferably, 25-39.5°C, more preferably, 25-39°C, and most preferably, 27.5-35°C). The term "cloud point" as used herein and in the appended claims refers to a well-known property associated with nonionic surfactant-containing aqueous formulations, whereby the solubility of the nonionic surfactant in the aqueous formulation decreases with increasing temperature of the formulation. The temperature at which the appearance of a second phase is observable in a given nonionic surfactant-containing aqueous formulation is referred to as the "cloud point temperature".

[0022] Preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0-50% by weight of an additive based on the aqueous hard surface cleaning formulation. Preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0-50% by weight of an additive selected from the group consisting of salts, builders, enzymes (e.g., proteases, amylases, lipases, cellulases), corrosion inhibitors, pH adjusters (e.g., acids), bleaching agents (e.g., sodium percarbonate, sodium perborate), bleach activators (e.g., tetraacetylethylenediamine (TAED)), bleaching catalysts (e.g., manganese(II) acetate, cobalt(II) chloride, bis(TACN) magnesium trioxide diacetate), abrasives, fragrances, antimicrobial agents (e.g., biocides), colorants (e.g., dyes), thickeners, foam stabilizers, foam boosters, chelating agents, hydrotropes, organic cosolvents, and mixtures thereof.

[0023] Preferably, the aqueous hard surface cleaning formulation of the present invention further comprises a salt. More preferably, the aqueous hard surface cleaning formulation of the present invention further comprises a salt selected from the group consisting of alkali metal halide salts (e.g., sodium chloride, potassium chloride), ammonium salts, nitrates, sulfates, nitrites, and mixtures thereof. Most preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0 to 20 wt. % (preferably, 0.1 to 20 wt. %, more preferably, 0.1 to 10 wt. %) of a salt based on the weight of the aqueous hard surface cleaning formulation, the salt selected from the group consisting of alkali metal halide salts (e.g., sodium chloride, potassium chloride), ammonium salts, nitrates, sulfates, nitrites, and mixtures thereof.

[0024] Preferably, the aqueous hard surface cleaning formulation of the present invention further comprises a builder. More preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0 to 50% by weight (preferably, 0.1 to 30% by weight, more preferably, 0.1 to 15% by weight) of a builder based on the weight of the aqueous hard surface cleaning formulation. Most preferably, the aqueous hard surface cleaning formulations of the present invention further comprise a builder, the builder being selected from the group consisting of inorganic builders (e.g., tripolyphosphates, pyrophosphates), alkali metal carbonates, borates, bicarbonates, hydroxides, zeolites, citrates, polycarboxylates, monocarboxylates, aminotrismethylene phosphonic acid, salts of aminotrismethylene phosphonic acid, hydroxyethane diphosphonic acid, salts of hydroxyethane diphosphonic acid, diethylenetriamine penta(methylene phosphonic acid), salts of diethylenetriamine penta(methylene phosphonic acid), ethylenediaminetetraethylene-phosphonic acid, salts of ethylenediaminetetraethylene-phosphonic acid, oligomeric phosphonates, polymeric phosphonates, and mixtures thereof.

[0025] Preferably, the aqueous hard surface cleaning composition of the present invention comprises a pH adjuster. More preferably, the aqueous hard surface cleaning composition of the present invention comprises a pH adjuster, the pH adjuster being selected from the group consisting of inorganic acids, inorganic bases, organic acids, organic bases, and mixtures thereof. Most preferably, the aqueous hard surface cleaning composition of the present invention comprises a pH adjuster, the pH adjuster being selected from the group consisting of at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, monoethanolamine, triethanolamine, aminomethylpropanol, aminomethylpropanediol, trimethamine, gluconic acid, lactic acid, citric acid, glycolic acid, acetic acid, propionic acid, succinic acid, glutaric acid, adipic acid, butanedioic acid, isoascorbic acid, ascorbatic acid, tartaric acid, and mixtures thereof.

[0026] Preferably, the aqueous hard surface cleaning formulation of the present invention further comprises a bleaching agent. More preferably, the aqueous hard surface cleaning formulation of the present invention comprises 0-10 wt. % (preferably, 1-5 wt. %, more preferably, 2-4 wt. %) of a bleaching agent based on the weight of the aqueous hard surface cleaning formulation. Most preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0-10 wt. % (preferably, 1-5 wt. %, more preferably, 2-4 wt. %) of a bleaching agent based on the weight of the aqueous hard surface cleaning formulation, the bleaching agent being selected from the group consisting of peracids, perborates, percarbonates, chlorine generating substances (e.g., sodium hypochlorite, chloroisocyanurates), hydrogen peroxide, a hydrogen peroxide source, and mixtures thereof.

[0027] Preferably, the aqueous hard surface cleaning formulation of the present invention further comprises a chelating agent. More preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0 to 20% by weight (preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, most preferably 1 to 5% by weight) of a chelating agent based on the weight of the aqueous hard surface cleaning formulation. Most preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0 to 20% by weight (preferably 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, most preferably 1 to 5% by weight) of a chelating agent based on the weight of the aqueous hard surface cleaning formulation, and the chelating agent is selected from the group consisting of the following: ethylenediaminetetraacetic acid, ethylenediaminetriacetic acid, ethylenediaminetetrapropionic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid; oxydisuccinic acid, iminodisuccinic acid, benzenehexacarboxylic acid, poly(meth)acrylic acid, polyacrylonitrile, ethylhexanoic acid ... and mixtures thereof.

[0028] Preferably, the aqueous hard surface cleaning formulation of the present invention further comprises a hydrotrope. More preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0-10 wt. % (preferably, 0.1-10 wt. %, more preferably, 0.5 wt. %-7.5 wt. %, most preferably, 1-5 wt. %) of a hydrotrope based on the weight of the aqueous hard surface cleaning formulation. Even more preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0-10 wt. % (preferably, 0.1-10 wt. %, more preferably, 0.5 wt. %-7.5 wt. %, most preferably, 1-5 wt. %) of a hydrotrope based on the weight of the aqueous hard surface cleaning formulation, the hydrotrope being selected from the group consisting of urea, monoethanolamine; diethanolamine; triethanolamine; and calcium, sodium, potassium, ammonium, and alkanolammonium salts of xylene sulfonic acid, toluene sulfonic acid, ethylbenzene sulfonic acid, and cumene sulfonic acid; and mixtures thereof. Even more preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0-10 wt. % (preferably, 0.1-10 wt. %, more preferably, 0.5 wt. %-7.5 wt. %, most preferably, 1-5 wt. %) of a hydrotrope based on the weight of the aqueous hard surface cleaning formulation, the hydrotrope being selected from the group consisting of sodium toluene sulfonate, potassium toluene sulfonate, sodium xylene sulfonate, ammonium xylene sulfonate, potassium xylene sulfonate, calcium xylene sulfonate, sodium cumene sulfonate, ammonium cumene sulfonate, and mixtures thereof. Most preferably, the aqueous cleaning formulation of the present invention further comprises 0-10 wt. % (preferably, 0.1-10 wt. %, more preferably, 0.5 wt. %-7.5 wt. %, most preferably, 1-5 wt. %) of a hydrotrope based on the weight of the aqueous cleaning formulation, the hydrotrope comprising sodium xylene sulfonate (preferably, sodium xylene sulfonate).

[0029] Preferably, the aqueous hard surface cleaning formulation of the present invention further comprises an organic co-solvent. More preferably, the aqueous hard surface cleaning formulation of the present invention further comprises 0 to 10 wt. % (preferably, 0.01 to 10 wt. %, more preferably, 1 wt. % to 8 wt. %, most preferably, 2.5 to 7.5 wt. %) of an organic co-solvent based on the weight of the aqueous hard surface cleaning formulation. Preferably, the organic co-solvent is miscible with water. More preferably, the organic co-solvent is one of the following: an aliphatic alcohol (e.g., C 1~6 Alkanol, C 1~6alkyl diols), monoalkylene glycol ethers (e.g., ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol t-butyl ether, propylene glycol propyl ether, propylene glycol n-butyl ether, propylene glycol t-butyl ether, propylene glycol methyl ether acetate, propylene glycol diacetate), polyalkylene glycol ethers (e.g., diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol n-butyl ether, diethylene glycol t-butyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol n-butyl ether, dipropylene glycol t -butyl ether, dipropylene glycol phenyl ether, dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, tripropylene glycol propyl ether, tripropylene glycol n-butyl ether, tripropylene glycol t-butyl ether), and mixtures thereof (preferably isopropanol, ethanol, 2-(2-butoxyethoxy)ethanol, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol t-butyl ether, dipropylene glycol methyl ether, dipropylene glycol propyl ether, dipropylene glycol n-butyl ether, and mixtures thereof, more preferably dipropylene glycol methyl ether).

[0030] Preferably, the aqueous hard surface cleaning composition of the present invention has a pH of 3.5 to 9.0 (preferably 4.0 to 8.0, more preferably 5 to 8, most preferably 6 to 8).

[0031] Preferably, the aqueous hard surface cleaning formulation of the present invention comprises less than 0.003 wt. % (preferably, <0.001 wt. %, more preferably, <0.0001 wt. %, and most preferably, below the detection limit) of at least one C based on the weight of the aqueous hard surface cleaning formulation. 8~18 It contains a quaternary ammonium salt having an alkyl group.

[0032] Preferably, the aqueous hard surface cleaning formulations of the present invention contain less than 0.05 wt. % (preferably, <0.01 wt. %, more preferably, less than 0.001 wt. %, even more preferably, <0.0001 wt. %, and most preferably, <detection limits) of a cationic biocide based on the weight of the aqueous hard surface cleaning formulation, the cationic biocide being selected from the group consisting of quaternary ammonium salts ("quats") and biguanide compounds. More preferably, the aqueous hard surface cleaning formulations of the present invention contain less than 0.05 wt. % (preferably, <0.01 wt. %, more preferably, less than 0.001 wt. %, even more preferably, <0.0001 wt. %, and most preferably, <detection limits) of a cationic biocide based on the weight of the aqueous hard surface cleaning formulation, the cationic biocide being selected from the group consisting of quaternary ammonium salts ("quats") and biguanide compounds, the biguanide compounds having the formula (III): [ka] (In the formula, X 1 and X 2 is independently selected from the group consisting of hydrogen, an aliphatic group, a cycloaliphatic group, an aromatic group, a substituted aliphatic group, a substituted aromatic group, a heteroaliphatic group, a heterocyclic group, and a heteroaromatic group; Y 1 and Y 2 are independently selected from the group consisting of an aliphatic group, an alicyclic group, an aromatic group, a substituted aliphatic group, a substituted aromatic group, a heteroaliphatic group, a heterocyclic group, and a heteroaromatic group; n is an average value of 2 to 20; Z 1 and Z 2 are independently selected from hydrogen and salt anions (e.g., halides, nitrates, sulfates) The biguanide compound has a weight average molecular weight of 500 to 2,000 daltons.

[0033] Preferably, the aqueous hard surface cleaning formulations of the present invention contain less than 0.01 wt. % (preferably <0.001 wt. %, more preferably <0.0001 wt. %, most preferably <the limit of detection) of a castor oil derivative based on the weight of the aqueous hard surface cleaning formulation, the castor oil derivative being represented by Formula IV and Formula V: [ka] and [ka] (In the formula, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , and R 15 are each independently selected from the group consisting of a -CH2CHO- group, a -CH2CH2CHO- group, a -CH2CH2CHO- group, a -CH2CH2CH2CHO- group, a -CH(CH3)CHO- group, a -CH2CH(CH3)O- group, a -CH(CH3)CH2CHO- group, a -CH2CH(CH3)CHO- group, and a -CH2CH2CH(CH3)O- group, each -CH2CHO- group; a, b, c, d, e, f, g, h, I, j, k, and m are each independently a number from 0 to 250, the average sum of a+b+c+d+e+f is 1 to 250, and the average sum of g+h+i+j+k+m is 1 to 250.

[0034] Preferably, the aqueous hard surface cleaning formulation of the present invention contains less than 0.5 wt. % or more than 3 wt. % (preferably <0.1 wt. % or more than 5 wt. %, more preferably <0.01 wt. %, even more preferably <0.001 wt. %, and most preferably below the detection limit) of a mixture of (a) an aminocarboxylic acid chelator and (b) a polycarboxylic acid chelator, based on the weight of the aqueous hard surface cleaning formulation, where the aminocarboxylic acid chelator is a chelating agent having a nitrogen atom and a carboxy group, and the polycarboxylic acid chelator is a chelating agent having at least two functional groups per molecule including at least one carboxy group, the functional groups being selected from carboxy groups and hydroxy groups (e.g., acetic acid, adipic acid, monochloroacetic acid, oxalic acid, succinic acid, oxydisuccinic acid, carboxymethylsuccinic acid, carboxymethyloxysuccinic acid, glycolic acid, diglycolic acid, lactic acid, tartaric acid, carboxymethyltartaric acid, citric acid, malic acid, gluconic acid, and salts thereof).

[0035] Preferably, the aqueous hard surface cleaning formulations of the present invention contain less than 0.5 wt. % (preferably, <0.1 wt. %, more preferably, <0.01 wt. %, even more preferably, <0.001 wt. %, and most preferably, below the detectable limit) of a compound of formula (VI): [ka] (wherein p is 1 or 2 (or p is 1 to 8))

[0036] Preferably, the aqueous hard surface cleaning formulations of the present invention contain less than 0.01 wt. % (preferably, <0.001 wt. %, more preferably, <0.0001 wt. %, and most preferably, below the limit of detection) of zwitterionic surfactant based on the weight of the aqueous hard surface cleaning formulation.

[0037] Preferably, the aqueous hard surface cleaning formulations of the present invention contain <0.01 wt. % (preferably <0.001 wt. %, more preferably <0.0001 wt. %, most preferably <limit of detection) of anionic surfactant based on the weight of the aqueous hard surface cleaning formulation.

[0038] Preferably, the method of cleaning a hard surface of the present invention comprises: selecting an aqueous hard surface cleaning formulation of the present invention; applying the aqueous hard surface cleaning formulation to a soiled hard surface having a substance to be removed (e.g., at least one of dirt, grease, oil); and rubbing the aqueous hard surface cleaning formulation onto the soiled hard surface (preferably using the aqueous hard surface cleaning formulation in conjunction with an implement) to provide a cleaned hard surface, wherein at least some of the substance to be removed has been removed.Preferably, the cleaned hard surface may be further rinsed with water.Preferably, the cleaned hard surface may be further rinsed with water and then dried.

[0039] Preferably, the aqueous hard surface cleaning formulations of the present invention are used in conjunction with an implement for cleaning hard surfaces. The implement may be primarily manual in nature (e.g., a handheld scrubbing brush) or may be at least partially motorized (e.g., a powered scrubbing device).

[0040] Preferably, the aqueous hard surface cleaning formulation is applied to the soiled hard surface by at least one of spraying, pouring, and pre-loading onto the equipment to be used in conjunction with the hard surface cleaning formulation.

[0041] Preferably, the aqueous hard surface cleaning formulation of the present invention is used in conjunction with an implement, and the implement is selected from the group consisting of at least one of brushes, mops, sponges, and woven or nonwoven fabrics or towels.Preferably, the implement comprises an absorbent / adsorbent material, such as a woven material (e.g., woven cotton fiber, woven cotton / nylon blended fiber), a nonwoven material (e.g., nonwoven fiber sheet material, such as meltblown material, spunbond material, coform material, wetlaid material, airlaid material, bonded carded material, web material, and hydroentangled material), a sponge / sponge-like material (e.g., natural sponge, regenerated cellulose, polyurethane foam).Preferably, the implement comprises an absorbent / adsorbent material, and the aqueous hard surface cleaning formulation is preloaded into the absorbent / adsorbent material before the aqueous hard surface cleaning formulation is contacted with the soiled hard surface.

[0042] The fibers in the nonwoven materials used in conjunction with the aqueous hard surface cleaning formulations of the present invention can include, for example, polyester fibers, rayon fibers, nylon fibers, polypropylene fibers, polyethylene fibers, cellulose fibers, and mixtures thereof.

[0043] Some embodiments of the present invention will now be described in detail in the following examples.

[0044] Comparative Examples C1 to C12 and Examples 1 to 2: Formulations Aqueous hard surface cleaning formulations were prepared according to Comparative Examples C1-C12 and Examples 1-2 by adding surfactant to water as specified in Table 2, shaking until dissolved, then adding solvent, if present, as specified in Table 2, and rolling on a bench top roller until dissolved.

[0045] Phase stability of formulations The phase stability of the aqueous hard surface cleaning formulations prepared according to Comparative Examples C1-C12 and Examples 1-2 was evaluated by storing the formulations at 21° C. for 20 days and observing the degree of phase separation, if any, present in the stored formulations. The evaluation results are provided in Table 2.

[0046] Turbidity The turbidity of the aqueous hard surface cleaning formulations prepared according to Comparative Examples C1-C12 and Examples 1-2 was measured using a turbidimeter at 21° C. after the formulations had been stored at 21° C. for at least 20 days. The instrument was calibrated according to the instructions provided with the machine. The turbidity measured in Nephelometric Turbidity Units (NTU) is provided in Table 2. [Table 2]

[0047] Comparative Examples C13 to C37 and Examples 3 to 5: Formulations Aqueous hard surface cleaning formulations were prepared according to Comparative Examples C13-C37 and Examples 3-5 by adding surfactant to water as specified in Table 3, shaking until dissolved, then adding solvent, if present, as specified in Table 3, and rolling on a bench top roller until dissolved.

[0048] Phase stability of formulations The phase stability of the aqueous hard surface cleaning formulations prepared according to Comparative Examples C13-C37 and Examples 3-5 was evaluated by storing the formulations at 21° C. for 20 days and observing the degree of phase separation, if any, present in the stored formulations. The evaluation results are provided in Table 3.

[0049] Cloud Point Temperature The cloud point temperatures of the aqueous hard surface cleaning formulations prepared according to Comparative Examples C13-C37 and Examples 3-5 were determined by placing 1 mL samples of the aqueous hard surface cleaning formulations in 1.5 mL clear glass vials and measuring the transmittance of light (at 645 nm) through the formulation as a function of temperature using a Technobis Crystallization Systems Crystal16. The cloud point temperature was recorded as the temperature at which the transmittance of light (at 645 nm) through the sample fell below 100%. The results are provided in Table 3.

[0050] Cleaning performance The cleaning performance of aqueous hard surface cleaning formulations prepared according to Comparative Examples C13-C37 and Examples 3-5 was determined using the following procedure. A tile (Premium Excelon Feature Tile & Strip, Chalk II 56830 / L597A available from ArmstrongFlooring) was soiled with 500 μL of naphtha and carbon black based soil. The soil was prepared by mixing 61.04 wt% Naptha 60 / 110, 27.6 wt% Vognis Myritol 318, 8.2 wt% soybean oil, and 3.18 wt% Mogyul L carbon black using a stir bar until all the carbon black was suspended. The soil was then applied to the center of the tile and smeared using a sponge applicator with 20 up and down movements while holding the tile at an angle of 45-90° to the ground. The tile was then left to dry overnight. The tiles were then placed in a device for holding non-porous substrates described in US Patent Publication No. 20100083778, the disclosure of which is incorporated herein by reference in its entirety, in which a removable well insert has 24 openings. Each opening was filled with 400 μL of an aqueous hard surface cleaning formulation and covered with a 3 mm needle punch carpet purchased from The Felt Store Inc. (West Seneca, NY) attached to a 12.7 g cone weight. The plate and tile were mechanically moved back and forth laterally relative to each other to scrub the tile surface for 5 minutes. The plate was then removed and the tile surface was rinsed with deionized water. The scrubbed tile surface was then analyzed using an EPSON Perfection V500 Photo Scanner and ImageJ software to extract the gray value of each well on the scrubbed tile for each formulation. The gray value of each scrubbed tile area was then compared to the gray values ​​measured for the original tile before soiling and the soiled area of ​​the tile before cleaning. Note that a value of 0% corresponds to a grey value equal to the grey value of the soiled area before cleaning, and a value of 100% corresponds to a grey value equal to the grey value of the original tile before soiling. The results are provided in Table 3. [Table 3]

Claims

1. 1. An aqueous hard surface cleaning formulation comprising: (a) water; (b) 0.1 to <5 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of a nonionic branched alcohol alkoxylate surfactant having a hydrophobic-lipophilic balance (HLB) of 0.5 to 11.5; (c) 0.01% to 25% by weight, based on the weight of the aqueous hard surface cleaning formulation, of a compound of formula (I): 【Chemistry 1】 and an ethoxylated phenol having the formula: said aqueous hard surface cleaning formulation having a weight ratio (c) / (b) of 0.1 to <5, said weight ratio being equal to the weight of said ethoxylated phenol (c) contained in said aqueous hard surface cleaning formulation divided by the weight of said nonionic surfactant (b) contained in said aqueous hard surface cleaning formulation; The aqueous hard surface cleaning formulation comprises less than 0.003 wt. % of at least one C ８～１８ Contains a quaternary ammonium salt having an alkyl group, the aqueous hard surface cleaning formulation contains less than 0.05 wt. % of a cationic biocide, based on the weight of the aqueous hard surface cleaning formulation, the cationic biocide being selected from the group consisting of quaternary ammonium salts and biguanide compounds; the aqueous hard surface cleaning formulation contains <0.01 wt. % of a castor oil derivative, based on the weight of the aqueous hard surface cleaning formulation; the aqueous hard surface cleaning formulation comprises <0.5 wt. % or >3 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of a mixture of (a) an amino carboxylic acid chelator and (b) a polycarboxylic acid chelator, the amino carboxylic acid chelator being a chelating agent having a nitrogen atom and a carboxy group, the polycarboxylic acid chelator being a chelating agent having at least two functional groups per molecule including at least one carboxy group, the functional groups being selected from carboxy groups and hydroxy groups; The aqueous hard surface cleaning formulation has less than 0.5 wt. %, based on the weight of the aqueous hard surface cleaning formulation, of formula (VI): 【Chemistry 2】 1. An aqueous hard surface cleaning formulation comprising the component:

2. 10. The aqueous hard surface cleaning formulation of claim 1, which is phase stable after storage at 21°C for 20 days.

3. 3. The aqueous hard surface cleaning formulation of claim 2 having a cloud point temperature of from 25°C to <40°C.

4. 4. The aqueous hard surface cleaning formulation of claim 3, wherein T is on average 3.25 to 8.

5. 4. The aqueous hard surface cleaning formulation of claim 3, wherein T is on average 3.5 to 7.

6. 4. The aqueous hard surface cleaning formulation of claim 3, wherein T is on average 3.75 to 6.

5.

7. additives selected from the group consisting of salts, builders, enzymes (e.g., proteases, amylases, lipases, cellulases), corrosion inhibitors, pH adjusters (e.g., acids), bleaching agents (e.g., sodium percarbonate, sodium perborate), bleach activators (e.g., tetraacetylethylenediamine (TAED)), bleach catalysts (e.g., manganese(II) acetate, cobalt(II) chloride, bis(TACN) magnesium trioxide diacetate), abrasives, fragrances, antimicrobial agents (e.g., biocides), colorants (e.g., dyes), thickeners, foam stabilizers, foam boosters, chelating agents, hydrotropes, organic cosolvents, and mixtures thereof; 5. The aqueous hard surface cleaning formulation of claim 4 further comprising:

8. 8. The aqueous hard surface cleaning formulation of claim 7, containing <0.01 wt. % zwitterionic surfactant, based on the weight of the aqueous hard surface cleaning formulation.

9. 9. The aqueous hard surface cleaning formulation of claim 8, containing <0.01 wt. % anionic surfactant, based on the weight of the aqueous hard surface cleaning formulation.

10. 1. A method for cleaning a hard surface comprising: Selecting an aqueous hard surface cleaning formulation according to claim 1; applying said aqueous hard surface cleaning formulation to a soiled hard surface having material to be removed; and scrubbing said aqueous hard surface cleaning formulation against said soiled hard surface to provide a cleaned hard surface, wherein at least some of said removed material has been removed.

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