Methods of reducing the foaming of acid-based cleaning compositions

Abstract

The present invention is directed to cleaning compositions comprising an acid and an alkylamine ethoxylate blend, methods of manufacturing and using such compositions, wherein the alkylamine ethoxylate blends used in formulating such composition has suitable concentrations of alkylamine ethoxylate A0EO, A1EO, and A2EO, to avoid extra foaming during the manufacturing process.

Description

[0001] METHODS OF REDUCING THE FOAMING OF ACID-BASED CLEANING COMPOSITIONS

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to a process for preparing a cleaning composition with low ethoxylated levels of alkylamine ethoxylates.

[0004] BACKGROUND OF THE INVENTION

[0005] The prior art is replete with hard surface cleaning compositions that are effective in the cleaning of variety of stains in bathrooms, kitchens, and other areas, particularly toilets bowls, showers, bathtubs, sinks, tiles, countertops, walls, floors and the like. Many of these cleaning compositions contain a combination of components including strong inorganic acids and / or organic acids, surfactants, wetting agents, solvents, and adjuvants that would address stains and / or build-ups of germs in such areas. The acid component is typically selected to address descaling of hard water stains, while the surfactant component is typically a detergent selected to attack soil and grease. Other additives typically either enhance performance or make a particular formulation more desirable from a visual or odor perspective.

[0006] While the process of combining such ingredients to formulate cleaning compositions are generally known to those of ordinary skill in the art, the scale up efforts in producing such compositions are not free of challenges. At least one unavoidable problem facing the commercial manufacturers of such cleaning compositions involves the undesirable foaming that occurs during the mixing and bottling stages of liquid cleaning compositions. This undesirable foaming is essentially the side-effect of the mixing, the shearing and then traveling of the cleaning compositions and the respective raw material from one vessel or equipment to another. This problem is particularly exacerbated at higher concentrations of surfactants, higher pressures between manufacturing equipment’s, higher degree of turbulence and mixer’s speed.

[0007] Undesirable inline foaming and bottling difficulties result in production lines shut offs for addressing the foaming which would subsequently lead to an overall down time, slower operation and productivity, inefficient energy usage, production delays, and higher economic burden. Therefore, there is a need to develop better and more sustainable manufacturing processes to address such shortcomings. SUMMARY OF THE INVENTION

[0008] The present invention addresses these shortcomings in the art.

[0009] In the first aspect, the present invention is directed to a method of manufacturing a cleaning composition containing an acid and an alkylamine ethoxylate comprising the step of forming a mixture by mixing an alkyl phenol selected from the group consisting of a propylated phenol, a butylated phenol, a butylated hydroxyanisole, an amylated phenol, a hexylated phenol, a heptylated phenol or a combination thereof, with a first amount of a blend of alkylamine ethoxylate comprising free alkylamine, alkylamine 1 ethoxylate (A1EO) and alkylamine 2 ethoxylate (A2EO), a sufficient amount of a quaternary ammonium compound and water until all ingredients are fully dissolved, wherein a molar ratio of alkyl phenol to hydrochloric acid of between 0.75-1.5 of said alkyl phenol to 9 -25 of hydrochloric acid is obtained, wherein the combined content of free alkylamine and A1EO is less than 5% w.r.t with respect to the total amount of alkylamine ethoxylate in the cleaning composition, preferably less than 3% w.r.t with respect to the total amount of alkylamine ethoxylate in the cleaning composition, and the viscosity of the manufactured composition is at least 1500 cP at 20° C at 20 RPM Brookfield viscometer RV spindle 3. In some preferred embodiments, the viscosity of the manufactured composition is between 1750 to 2250 cps.

[0010] In some embodiments, the method according to the first aspect of the invention may optionally further comprising adding a second amount of a blend of alkylamine ethoxylate to the mixture.

[0011] In some embodiments, the content of free alkylamine, A1EO, A3EO, A4EO or and / or A5EO in the blends of alkylamine ethoxylate is measured prior to mixing with the alkyl phenol. In other embodiments, the content of free alkylamine is less 1.0%, preferably less than 0.5%, more preferably less than 0.25%. In another embodiment, the content of the A1EO is less than 3%, preferably less than 2.5%, more preferably less than 1.0% and most preferably less than 0.4%. In some embodiments, the blends of alkylamine ethoxylate may be free of the alkylamine, A1EO, alkylamine 3 ethoxylate (A3EO), alkylamine 4 ethoxylate (A4EO) and / or alkylamine 5 ethoxylate (A5EO).

[0012] In other embodiments, a sample of the cleaning composition is drawn and the content of the free alkylamine ethoxylate and the A1EO is measured, and adjusted so that the content of free alkylamine is less 1%, preferably less than 0.5%, more preferably less than 0.1% and the content of the A1EO is less than 3%, preferably less than 2.5%, more preferably less than 1.5% and most preferably less than 0.4%.

[0013] In some embodiments, the method according to the first aspect of the present invention further comprise the step of having the cleaning composition travel down at least one conduit into a bottle under a pressure ranging between 1.0 to 1.5 bar, preferably 1.2 to 1.3 bar. In some embodiments, the method according to the present invention is performed for a period of 90 to 300 minutes at temperatures ranging between 20 to 30 ° C.

[0014] In some embodiments, the quaternary ammonium is alkyl trimethyl ammonium chloride.

[0015] In some embodiments, the alkyl phenol is 2- propylphenol, di propyl phenol, butylhydroxytoluene, dibutylhydroxytoluene, methylamylphenol, or any combinations thereof. In other embodiments, the molar ratio of alkyl phenol to hydrochloric acid is between 0.9-1.25 of said alkyl phenol to 12-22.5 of hydrochloric acid, preferably between 0.95- 1.15 of said alkyl phenol to 15-19 of hydrochloric acid. In some embodiments, the viscosity of the manufactured composition is in the range between 1650 to 3000 cP, preferably 1750 to 2250 cP at 20°C at 20 RPM Brookfield viscometer RV spindle 3.

[0016] In some embodiments, the amount of the blend of alkylamine ethoxylate ranges between 10 kg to 7000 kg, preferably between 50 kg to 6000 kg, more preferably between 100 kg to 5000 kg. In other embodiments, the step (a) according to the present invention is performed at temperature ranging between 30°C to 75° C, preferably in the range of 45°C to 65° C.

[0017] In some embodiments, the quaternary ammonium compounds are selected from mono- long-chain, tri-short-chain, tetraalkyl ammonium compounds, di-long-chain, di-short-chain tetraalkyl ammonium compounds, trialkyl, mono-benzyl ammonium compounds, and mixtures thereof.

[0018] In the second aspect, the invention is directed to a cleaning composition comprising: (a) an acid at concentrations ranging between 0.5 to 30%, preferably 5 to 15%, (b) a butylated phenol and (c) a blend of alkylamine ethoxylate comprising free alkylamine, A1EO, A2EO, wherein the combined content of free alkylamine and A1EO is less than 5%, preferably less than 3, and (d) a sufficient amount of quaternary ammonium, wherein the molar ratio of a butylated phenol to acid in said composition is between 0.75-1.5 of said butylated phenol to 9 -25 of hydrochloric acid, and further wherein viscosity of the composition is at least 1500 cP at 20 ° C at 20 RPM Brookfield viscometer RV spindle 3. In some embodiments, the viscosity ranges between 1750 to 2250 cps, preferably 2100 cps. In some embodiments, the acid is selected from the group consisting of hydrochloric acid, citric acid, sulfuric acid, formic acid and any combinations thereof.

[0019] In the third aspect, the present invention is directed to cleaning compositions produced by the process of manufacturing according to the second aspect of the present invention, wherein the cleaning composition comprise (a) an acid at concentrations ranging between 0.5 to 30%, preferably 5 to 15%, (b) a butylated phenol and (c) a first blend of alkylamine ethoxylate comprising free alkylamine, A1EO, and A2EO, wherein the combined content of free alkylamine and A1EO is less than 5%, preferably less than 3, and (d) an amount of quaternary ammonium, wherein the molar ratio of a butylated phenol to acid in said composition is between 0.75-1.5 of said butylated phenol to 9 -25 of hydrochloric acid, and further wherein viscosity of the composition is at least 1500 cP at 20 ° C at 20 RPM Brookfield viscometer RV spindle 3,20 rpm. In some embodiments, the acid is selected from the group consisting of hydrochloric acid, citric acid, sulfuric acid, formic acid and any combinations thereof. In preferred embodiments, the content of free alkylamine is less 1%, preferably less than 0.5%, more preferably less than 0.1% and the content of the A1EO is less than 3%, preferably less than 2.5%, more preferably less than 1.5% and most preferably less than 0.4%. In some embodiments, the blend may be free of the alkylamine, A1EO, A3EO, A4EO or and / or A5EO. In some embodiments, the quaternary ammonium compounds are selected from mono-long-chain, tri-short-chain, tetraalkyl ammonium compounds, di-long-chain, di-short-chain tetraalkyl ammonium compounds, trialkyl, monobenzyl ammonium compounds, and mixtures thereof.

[0020] In the fourth aspect, the present invention is directed to method of cleaning a hard surface comprising applying the composition according to the first or third aspect of the present invention to the hard surface of interest followed by application of sufficient amount of water. In some embodiments, the hard surface is selected from material selected from the group consisting of bricks, ceramic, crystal, diamond, glass, latex, pebbles, porcelain, polymeric, wood tiles, quarry tiles, and natural stone. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1. is the bar graph indicating the ethoxylation degree of various source (A-G) of poly ethoxylated tallow amine products using liquid Chromatography coupled with High Resolution Mass Spectrometry (LC-HRMS), with a thermos biobasic column C4 50x2.1mm 5 pm.

[0022] DETAILED DESCRIPTION OF THE INVENTION

[0023] The disclosure relates to the viscous liquid hard surface cleaning compositions and methods of using such compositions to remove stains, soil or oil deposits in inclined hard surfaces and methods of using the same.

[0024] Definitions:

[0025] To facilitate understanding of the disclosure set forth herein, a number of terms are defined below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs and shall be understood to have the meanings described below. All publications and patents referred to herein are incorporated by reference in their entirety. Unless otherwise specified, a reference to a particular compound includes all ionic, salt, solvate, protected forms, and other stereoisomers thereof, isomeric forms, including racemic and other mixtures thereof.

[0026] As used herein, "about" will mean up to plus or minus 1% of the respective term.

[0027] As used herein, "consisting essentially of' refers to the combination of ingredients listed in the claim and excludes addition of any active ingredients to the combination. It also excludes addition of any excipient that materially affect the basic and novel properties of the composition.

[0028] The term "sufficient amount" as used herein, pertains to that amount of an active compound, raw material, or composition according to the present invention which is adequate for producing the desired results in a given manufacturing step or the intended cleaning and / or disinfecting effects including germicidal and reduction of bacterial load and / or the microorganism cell count.

[0029] As used herein with reference to carbon chains of a molecule, “long” chain is meant about Ce-3o alkyl, while “short” chain is meant C1-5 alkyl, preferably C1-3. The term "foam", "foamy", or "foaming" refers to a mass of frothy bubbles of air or gas in a matrix of liquid film such as a water surface that expands in size over time.

[0030] The term "hard surface" is meant to include all variations of hard surface areas including but not limited to areas that are made of such material as bricks, ceramic, cement, crystal, diamond, glass, latex, marble, metallic, pebbles, porcelain, polymeric and quarry tiles, and natural stone.

[0031] The term "surfactant system" refers to a single or combination of surfactant(s) selected from any such category of surfactants such as non-ionic, anionic, cationic, and amphoteric surfactants.

[0032] By the term "substantially free," is meant that the final product contains less than 0.5% weight of the identified ingredient, while by the term “free,” it is meant that the final product is free of any traces of the identified ingredient to the extent that it could be detected by general quantitative assays known in the art for detection of such ingredient in the final product or if detected, it is in residual content of the ingredient and in principle only attributable to impurities.

[0033] The term "treatment" as used herein in the context of applying or treating the desired surface to the extent that positive benefits are observed.

[0034] Methods of Manufacturing a cleaning composition

[0035] Alkylamine ethoxylates have many applications in the cleaning industry. They are used as thickeners, surfactants, or viscosity modifiers, in compositions such as detergent systems, toilet bowl cleaners, degreasers, anti-static agents, and the like. Alkylamine ethoxylates possess a surfactant structure which is composed of the lipophilic groups and the hydrophilic groups (polyalkylene oxide). The performance of alkylamine ethoxylates is dependent on a balance between the lipophilicity and the hydrophilicity provided by these groups. Such structure allows these compounds to act as a non-ionic surfactant in many cleaning and soap containing compositions and they are typically used in that capacity when included in a cleaning composition.

[0036] Traditionally, these materials are prepared from the base-catalyzed alkoxylation of the corresponding alkylamines. Such an alkoxylation reaction is actually the polymerization reaction of alkylene oxide, including the characteristic propagation and chain transfer steps of the polymerization process. For this reason, the resulting alkylamine ethoxylates are not a pure and single compound, rather a mixture of units having different degree of alkoxylation. The degree and concentration of different ethoxylated homologs may impact the properties of the corresponding blends of alkylamine ethoxylates.

[0037] US 8,049,039 described for example a two stage process of manufacturing a homolog distribution of ethoxylated alkylamine prepared from the regular (hydroxide-catalyzed) ethoxylation of alkylamine with 5 moles of ethylene oxide resulting in ethoxylated products. However, the process still failed to produce a single compound. Even though, in a commercial scale production of cleaning compositions, the use of pure single ethoxylated alkylamine compounds may be preferred, realizing such source is not readily sustainable.

[0038] The inventors of the present invention have now determined that depending on the distribution of the lower or higher degree of ethoxylation, alkylamine ethoxylate products impact the viscoelastic properties of cleaning compositions in relatively unpredictable manner, particularly when they are added into acid-based cleaning composition. Accordingly, they have observed that during the processes of manufacturing a cleaning composition and under certain manufacturing conditions, using different blends of alkylamine ethoxylate compounds provide undesired amount of in-line foaming, particularly different degree of ethoxylated amines provide different degree of undesired characteristics during the manufacturing of acid-based cleaning compositions. Therefore, at least in some aspects, the present invention is directed to optimizing the ratios and distribution of different ethoxylated amines in a blend of ethoxylated amine compounds to minimize the in-line foam production that occurs during the manufacturing process of an acid-based cleaning composition that may require ethoxylated tallow amines.

[0039] The levels of one or more of these undesirable components have a direct correlation with the unwanted degree of foaming when certain alkylamine ethoxylates are used as one of the components of cleaning compositions. The inventors have now identified that removal of the above identified undesirable components is particularly beneficial for the manufacturing process of a cleaning composition that contains an acid. Thus, in at least one aspect, the present invention is directed to a method of manufacturing an acid based cleaning composition that contains an alkylamine ethoxylates, such method includes the steps of mixing an alkyl phenol selected from the group consisting of a propylated phenol, a butylated phenol, a butylated hydroxyanisole, an amylated phenol, a hexylated phenol, a heptylated phenol or a combination thereof, a blend of alkylamine ethoxylate comprising free alkylamine, alkylamine 1 ethoxylate (A1E0) and alkylamine 2 ethoxylate (A2E0), wherein the combined content of free alkylamine and A1E0 is less than 5% w.r.t with respect to the total amount of alkylamine ethoxylate in cleaning compositions, preferably less than 3% w.r.t with respect to the total amount of alkylamine ethoxylate in cleaning compositions, a sufficient amount of hydrochloric acid and a sufficient amount of a quaternary ammonium. In some embodiments, the molar ratio of alkyl phenol to hydrochloric acid is between 0.75-1.5 of said alkyl phenol to 9 -25 of hydrochloric acid, and the viscosity of the manufactured composition is at least 1500 cP at 20° C at 20 RPM Brookfield viscometer RV spindle 3, preferably between 1750 to 2250 cps.

[0040] At least another aspect of the present invention is directed improving manufacturing processes of ethoxylated derivatives by implementing steps to limit the content of such desired by-products in the final commercial scale bulk volumes. For example, undesirable alkylamine ethoxylate by products or the level of vinyl ether ethoxylates or both, may be reduced substantially by incorporating a step of adding small amounts (e.g., in some embodiments 1 weight percent or less) of an acid to a reactor wherein such alkylamine ethoxylate compounds are prepared. In other embodiments, an additional step may be included where the degree of ethoxylation is assessed in the final product or in mid-stream processing of such final ethoxylated amine compound by using HPLC, gas chromatography and / or mass spectrometry. In some embodiments, liquid chromatography coupled with High Resolution Mass Spectrometry (LC-HRMS) or Tandem Mass Spectrometry (LC-MS-MS) may be used to determine the degree of ethoxylation in each of the source material or mid-stream compositions.

[0041] In some embodiments, the method according to the present invention further comprising step of adding a second amount of the blend of alkylamine ethoxylate. In some embodiments, the blend of alkylamine ethoxylate may be free of the alkylamine, A1EO, A3EO, A4EO and / or A5EO. In some embodiments, the content of alkylamine, and the degree of ethoxylation for different alkylamine ethoxylates are measured during the process of manufacturing and / or before adding such blends into the respective mixtures. In some embodiments, the total amount of free alkylamine and A1EO is less than 5%. In some embodiment, the degree of ethoxylation of all ingredients in the alkylamine ethoxylate blend is assessed before mixing the first ethoxylate blend with alkylphenol and the acid in the methodology described above. Accordingly, in some embodiments, the content of free alkylamine in the source of alkylamine ethoxylate is less 1%, preferably less than 0.5%, more preferably less than 0.1%. In other embodiments, the content of the A1EO of the source raw material may be less than 3%, preferably less than 2.5%, more preferably less than 1.5% and most preferably less than 0.4%. In some embodiments, the degree of ethoxylation of all ingredients in the second alkylamine ethoxylate blend is measured before mixing the second ethoxylate blend into the respective mixtures.

[0042] In other embodiments, the method further comprising the step of allowing the cleaning composition to travel down at least one conduit into a bottle under a pressure ranging between 1.0 to 1.5 bar, preferably 1.2. In some embodiments, the method is performed for a period of 90 to 300 minutes at temperatures ranging between 20 to 30 ° C.

[0043] In other embodiments, the molar ratio of alkyl phenol to hydrochloric acid is between 0.9-1.25 of said alkyl phenol to 12-22.5 of hydrochloric acid, preferably between 0.95- 1.15 of said alkyl phenol to 15-19 of hydrochloric acid. In some embodiments, the viscosity of the manufactured composition is at least 1500 cps, or in the range between 1650 to 3000 cP, preferably 1750 to 2250 cP at 20°C at 20 RPM Brookfield viscometer RV spindle 3.

[0044] In some embodiments, the amount for the blend of alkylamine ethoxylate ranges between 10 kg to 6000 kg, preferably between 50 kg to 3000 kg, more preferably between 100 kg to 1750 kg.. In other embodiments, the step (a) according to the present invention is performed at temperature ranging between 30 to 75 ° C, preferably in the range of 45 to 65 ° C.

[0045] In some embodiments, the preferred quaternary ammonium compounds are selected from mono-long-chain, tri-short-chain, tetraalkyl ammonium compounds, di-long-chain, di-short- chain tetraalkyl ammonium compounds, trialkyl, mono-benzyl ammonium compounds, and mixtures thereof. In some embodiments, the alkyl phenol is 2- propylphenol, di propyl phenol, butylhydroxytoluene, dibutylhydroxytoluene, methylamylphenol, or any combinations thereof.

[0046] In other embodiments, the method includes a step of measuring the content of any one free of the alkylamine, A1EO, A3EO, A4EO or and / or A5EO. Such measurement can be done at the time of obtaining the alkylamine ethoxylate from the primary source or prior adding the alkylamine ethoxylate blend to the alkylphenol or the acid or during the process of manufacturing of the cleaning composition. For example, in some embodiments, a sample from the mixture of alkyl phenol, alkylamine ethoxylate and acid is drawn and the content of free alkylamine and A1E0 is measured. As such, in preferred embodiments, the content of free alkylamine should be less than 1%, preferably less than 0.5%, more preferably less than 0.1% and the content of the A1EO should be less than 3%, preferably less than 2.5%, more preferably less than 1.5% and most preferably less than 0.4%. In some embodiments, the blend may be free of the alkylamine, A1EO, A3EO, A4EO or and / or A5EO.

[0047] Compositions

[0048] The compositions according to the invention are easily produced by any of a number of known art techniques. The list of raw material in compositions according to the present invention are described below:

[0049] 1. ACIDIC COMPONENT

[0050] Exemplary acids may be an inorganic acid or an organic. The inorganic acids suitable for the compositions according to the present invention include but not limited to hydrochloric acid, sulfuric acid, phosphoric acid, potassium dihydrogenphosphate, sodium dihydrogenphosphate, sodium sulfite, potassium sulfite, sodium pyrosulfite (sodium metabisulfite), potassium pyrosulfite (potassium metabisulfite), acid sodium hexametaphosphate, acid potassium hexametaphosphate, acid sodium pyrophosphate, acid potassium pyrophosphate, sulfamic acid, and suitable acid salts thereof; and any combinations thereof, preferably hydrochloric acid or sulfuric acid.

[0051] Exemplary organic acid suitable for the compositions according to the present invention include but are not limited to formic acid, acetic acid, propionic acid, butyric acid and valeric acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid and maleic acid; acidic amino acids including glutamic acid and aspartic acid; and hydroxy acids including glycolic acid, lactic acid, hydroxyacrylic acid, alphahydroxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid and citric acid, as well as acid salts thereof; preferably citric acid, cresylic acid, dodecylbenzene sulfonic acid, phosphoric acid, salicylic acid, sorbic acid, sulfamic acid, acetic acid, benzoic acid, boric acid, capric acid, caproic acid, cyanuric acid, dihydroacetic acid, dimethylsulfamic acid, polyacrylic acid, 2-ethyl-hexanoic acid, fumaric acid, I-glutamic acid, isopropyl sulfamic acid, naphthenic acid, oxalic acid, phosphorous acid, valeric acid, benzene sulfonic acid, xylene sulfonic acid, sulfonic acids, maleic acid, acetic acid, adipic acid, formic acid, lactic acid, butyric acid, gluconic acid, malic acid, tartaric acid, and glycolic acid.

[0052] In more preferred embodiments, the acid source is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, fumaric acid, maleic acid; glycolic acid, and citric acid, and salts thereof. These acids can be used singly or as a mixture of two or more. Of these acids, hydrochloric acid, sulfamic acid, citric acid, formic acid, oxalic acid, and fumaric acid are particularly preferred for use as the sole acid source. Of lesser preference mixtures comprising any combination of such acids are also included.

[0053] While the acids may be present in any effective amount in order to attain a desired acidic pH, they are present in an amount of from about 0.2% weight to about 40% weight, but preferably from 0.5% to 15% weight, based on the total weight of the compositions of which they form a part. In certain preferred embodiments of the invention the sole acid present is hydrochloric acid, citric acid, formic acid, oxalic acid, and fumaric acid, and salts thereof.

[0054] The cleaning composition according to the present invention may have a viscosity ranging between 1750 cP to 2250 cP, exhibiting a pH of about 5 or less. In some embodiments, the compositions contains at least one inorganic and / or one organic acid in sufficient amounts to have a pH of 4 or less, preferably a pH of 3.8, 3.5, 3.25, 3.0, 2.75, 2.5, 2.25, 2, 1.75, 1.5, 1.25, 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, and 0.1 or lower.

[0055] 2. SURFACTANTS

[0056] Among variety of suitable nonionic surfactants that may be included in the composition according to the present invention, alcohol ethoxylates (AEOs) and alkylamine ethoxylates (ANEOs) are most one essential non-ionic that may be present in the cleaning composition in the form of a blend including free of the alkylamine, A1EO, A3EO, A4EO and / or A5EO. In some embodiments the blend of ethoxylated alkylamines may include free alkylamine ethoxylate, A1EO and A2EO, wherein the combined content of free alkylamine ethoxylate and A1EO is less than 5%, preferably less than 3%.

[0057] In other embodiments, the content of A2EO is more than 95% of the blend, preferably more than 97.5 %, and ideally more than 98% of the entire content of the ethoxylated alkylamine source. In some embodiments, the total amount of free alkylamine and A1E0 is less than 5%, preferably less than 3%, more preferably less than 2%. In some embodiments, each of the free alkylamine or A1E0 are present in the ethoxylated alkylamine source in amounts less than 2%, preferably less than 1% by weight.

[0058] In some embodiments, the compositions according to the present invention may further include anionic, cationic as well as amphoteric surfactant generally in sufficient amounts to provide their intended purpose, ranging between at least 1% wt. to about 15% wt, and preferably the total amount of surfactants present in the inventive compositions does not exceed about 35% wt., more preferably does not exceed about 25% wt, and most preferably does not exceed 10%.

[0059] Examples of Cationic surfactants include: Quaternary ammonium compounds are selected from mono-long-chain, tri-short-chain, tetraalkyl ammonium compounds, di-long-chain, di-short-chain tetraalkyl ammonium compounds, trialkyl, mono-benzyl ammonium compounds, and mixtures thereof.

[0060] OPTIONA INGREDIENTS

[0061] In some embodiments, the present composition may include one or more additional optional ingredients selected from the group consisting of dye, a fragrance, fragrance adjuvant, a chelating agent, bleaching agent, oxidizing agents, film forming materials, preservatives, bitterness flavorant, antioxidants, radical scavengers, hydrotropes, thickeners, anticorrosion agents, solvents, opacifiers, brighteners, abrasives such as silica, kaolin, talc or an absorbent. Such ingredients as described above include known art compositions, including those described in McCutcheon's Detergents and Emulsifiers, North American Edition, 1998; Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., Vol. 23, pp. 478-541, the contents of which are herein incorporated by reference.

[0062] Suitable dyes and pigments that may be used in this invention include, but are not limited to Sanolin Blue EHRL, Sanolin Blue NBL, Sanolin Lave Blue A liq, Sanolin Tartrazine X 90 and Sanolin Quinoline Yellow 70 (Clariant), Acid blue or red dyes, such as Acid blue 80 CI 61585 and Acid Red 52 CI 45100, or the like such as CI Direct dyes as well as FD&C approved colorants. Suitable fragrances that may be used in this invention includes naturally derived from plant and / or animal or synthetic fragrances including but not limited to essential oils derived from herbs, flowers, trees, and other plants. Such oils include for example, rose oil or peppermint oil, sesame oil, macadamia nut oil, tea tree oil, evening primrose oil, Spanish sage oil, Spanish rosemary oil, coriander oil, thyme oil, pimento berries oil, rose oil, anise oil, balsam oil, bergamot oil, rosewood oil, cedar oil, chamomile oil, sage oil, clary sage oil, clove oil, cypress oil, eucalyptus oil, fennel oil, sea fennel oil, frankincense oil, geranium oil, ginger oil, grapefruit oil, jasmine oil, juniper oil, lavender oil, lemon oil, lemongrass oil, lime oil, mandarin oil, marjoram oil, myrrh oil, neroli oil, orange oil, patchouli oil, pepper oil, black pepper oil, petitgrain oil, pine oil, rose otto oil, rosemary oil, sandalwood oil, spearmint oil, spikenard oil, vetiver oil, wintergreen oil, or the like known to those of skill in the art. Preferred fragrances include Dynamo 20 (I.F.F) or Marine 20 TBC T11036681 (Takasago).

[0063] Generally fragrances and perfumes are complex mixtures or blends various organic compounds including, but not limited to, certain alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils such as from about 0 to about 85% by weight, usually from about 10 to about 70% by weight, the essential oils themselves being Volatile odiferous compounds and also functioning to aid in the dissolution of the other components of the fragrance composition. Examples of such fragrances include digeranyl Succinate, dineryl Succinate, geranyl neryl Succinate, geranyl phenylacetate, neryl phenylacetate, geranyl laurate, neryl laurate, di(b-citronellyl)maleate, dinonadol maleate, diphenoxyanol maleate, di(3.7- dimethyl-l-octanyl)succinate, di(cyclohexylethyl)maleate, diflralyl Succinate, di(phenylethyl)adipate, 7-acetyl-l,2,3,4, 5,6,7,8-octahydro-l,l,6,7-tetramethyl naphthalene, ionone methyl, ionone gamma methyl, methyl cedrylone, methyl dihydrojasmonate, methyl l,6,10-trimethyl-2.5.9-cy clododecatrien-l-yl ketone, 7-acetyl-l,l,3,4,4,6-hexamethyl tetralin, 4- acetyl-6-tertbutyl-l-, 1 -dimethyl indane, para-hydroxy-phenyl-butanone, benzophenone, methyl beta-naphthylketone, 6-acetyl-l,l,2,3,3,5hexamethylindane, 5-acetyl3 -isopropyl- 1,1, 2,6- tetramethyl indane, 1-dodecanal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-l- carboxaldehyde,7-hydroxy-3,7-dimethylocatanal, 10-undecen-l-al, isohexenyl cyclohexylcarboxaldehyde, formyl tricyclodecane, condensation products of hydroxy citronellal and methyl anthranilate, condensation products of hydroxycitronellal and indol, condensation products of phenyl acetaldehyde and indol, 2-methyl-3-(para-tert-butylphenyl)- propionaldehyde, ethyl Vanillin, heliotropin, hexyl cinnamic aldehyde, amylcinnamic aldehyde, 2-methyl-2-(para-iso-propylphenyl)propionaldehyde, coumarin, decalactone gamma, cyclopentadecanolide, 16-hydroxy-9-hexadecenoic acid lactone, 1.3.4.6.7.8-hexahydro- 4,6,6,7,8,8-hexamethylcyclopenta-gamma2-b-enzopyrane, beta-naphthol methyl ether, ambroxane, dodecahydro-3 a, 6, 6, 9a-t-etramethylnaphtho2. Iblfuran, cedrol, 5-(2,2,3- trimethylcyclopent-3-enyl)-3-methylpentan-2-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-l-yl)- 2-bute-n-l-ol, caryophyllene alcohol, tricyclodecenyl propionate, tricyclodecenyl acetate, benzyl salicylate, cedrylacetate, para-(tert-butyl)cyclohexyl acetate, essential oils, resinoids, and resins from a variety of sources including but not limited to orange oil, lemon oil, patchouli, Peru balsam, Olibanum resinoid, Styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander, lavandin, and lavender, phenylethyl alcohol, terpineol, linalool, linallyl acetate, geraniol, nerol, 2-(l,l-dimethylethyl)cyclohexanol acetate, benzylacetate, orange terpenes, eugenol, diethylphthalate, and combinations thereof. In the present invention, the precise composition of the fragrance is of no particular consequence so long as it may be effectively included as a constituent of the compositions, and have a pleasing fragrance. Two preferred fragrances include terpene alcohols which are effective to provide a pine-type scent, or a citrus-type scent depending upon its source and / or composition, as well as methyl salicylate.

[0064] Fragrance compositions as received from a supplier may be provided as an aqueous or organically solvated composition, and may include as a hydrotrope or emulsifier or a surfactant, in minor amount, generally not in excess of about 1.5% wt. Such fragrance compositions are quite usually proprietary blends of many different specific fragrance compounds. However, one of ordinary skill in the art, by routine experimentation, may easily determine whether such a proprietary fragrance composition is compatible in the compositions of the present invention.

[0065] Such fragrances may be added in any conventional manner, admixing to a composition, or blending with other constituents used to form a composition, in amounts which are found to be useful to enhance or impart the desired scent characteristic to the composition, and / or to cleaning compositions formed therefrom.

[0066] Film forming material such as polyethylene oxides or mixed polyethylene oxidespolypropylene oxides having molecular weights in excess of about 50,000 and if present, desirably having molecular weights in the range of from about 100,000 to about 8,000,000 may also be useful in the present compositions. According to particularly desirable embodiments of the invention, the film-forming constituent of the present invention is solely a water soluble polyethylene oxide. The polyvinylpyrrolidone polymers useful in the present inventive compositions exhibit a molecular weight of at least about 5,000, with a preferred molecular weight of from about 6,000-3,000,000.

[0067] High molecular weight polyethylene glycol polymers useful in the present inventive compositions exhibit a molecular weight of at least about 100, preferably exhibits a molecular weight in the range of from about 100 to about 10,000 but most preferably a molecular weight in the range of from about 2000 to about 10,000. Particularly useful high molecular weight . Polyethylene glycols are available under the tradename Carbowax® (ex. Dow) or other suppliers of high molecular weight polyethylene glycols.

[0068] METHODS OF USE

[0069] At least one aspect of the present invention is directed to apply the compositions according to the present invention in inclined hard surfaces to provide maximum coverage. In some embodiments, the surface is rinsed after application of the cleaning composition to the surface after sufficient amount of time allowing the composition to come in contact with the stain or soils of interest to remove them from the surface.

[0070] In some embodiments, the composition of the present invention is able to achieve a degree of germ kill allowing sufficient time for the composition to come in direct contact with the hard surfaces of interest, achieving at least a twofold reduction of the bacterial load (number of bacterial cells) of at least any three species of Enterococcus hirae, Escherichia Coli, Staphylococcus aureus and Pseudomonas aeruginosa. In some embodiments, the compositions of the present invention achieve a 4-log reduction of the bacterial load of all such species. In some embodiments, the compositions of the present invention achieve a 5-log reduction of the bacterial load of all such species as measured by appropriate EN standards tested for antimicrobial activity under European test methods such as EN 13697 and EN1276 for evaluating antimicrobial efficacy of compositions.

[0071] An example formulation illustrating an embodiment of the inventive cleaning composition of the present invention is described in detail below and was formulated generally in accordance with the following protocol. EXAMPLES

[0072] Example 1- PREPARATION OF THE CLEANING FORMULATION

[0073] An acid containing cleaning composition was prepared following the steps of adding in a clean and empty first vessel, an amount of about 1.6 to 1.9 kg of butylated hydroxytoluene (BHT), about 145 to 150 kg of a blend of amine ethoxylated containing alkylamine ethoxylate (A2EO), free alkylamine, and alkylamine 1 ethoxylate (A1EO), mixing the components at a temperature of about 40 to 65° C to help with the solubility until a uniform mixture is obtained.

[0074] The resulting mixture is then added to about 75 to 85 litters of water and desired dyes ranging between 4 to 8 Kg to formulate the dye solution. Then about 40 to 45 litters of a dye solution with the BHT / alkylamine ethoxylate blend mixture is added while continue to stir slowly until a uniform mixture is obtained. About 75 to 80 Kg of hydrochloric acid is added to the mixture while mixing for additional 10-15 minutes until a homogenous mixture is obtained.

[0075] To the homogenous mixture containing hydrochloric acid, add about 110 to 115 Kg of an alkyl trimethyl ammonium chloride and continue stirring until a uniform mixture is obtained. Fragrance and other ingredients may be added at this point to finalize the cleaning composition. If necessary, pump the surfactant out and replace with a second blend of alkylamine ethoxylate through the bottom of the vessel. The homogenous mixture then travelled down under pressure of about 1.2 bar to a bottling system. Undesirable foaming was observed complicating the filing of the bottle with the desired volume of the cleaning composition, which required shutting of the system and addressing the problem.

[0076] Example 2- DETERMINING THE ROLE OF FREE ALKYL AMINE AND / OR AE1O IN UNDESIRABLE FOAMING

[0077] The same process as in Example 1 was followed except that prior to adding the ethoxylated amine source into the first vessel of Example 1, the content of free alkylamine, A1EO, A2EO, A3EO and A4EO were measured to evaluate the effect of each homolog on the extent of foaming during the manufacturing of the cleaning composition. Using liquid Chromatography coupled with High Resolution Mass Spectrometry (LC-HRMS) (See Figure 1), the degree of ethoxylation in each of the source material (A) to (G) was evaluated. The analysis revealed that among the tested sources (A) to (G), the source that exhibited undesirable viscosity and / or foaming was richer in free alkylamine, A1E0, A3EO and A4EO. Further, the lower the level of A2EO the poorer the performance. Among all sources of alkylamine ethoxylate compounds, source (A) gave the most foam and bottling problems during the manufacturing process because of sub-optimal ethoxylation. Since source materials other than (A) had higher proportion of A3E0 and A4E0 (see Figure 1), it was concluded that the foaming is primarily due to the presence of free alkylamine AOEO and A1E0. Additionally, drop in viscosity was also contributed by relatively higher proportions of free alkylamine and A1E0.

[0078] It was thus determined that the optimal concentration of A2E0 in the homolog blend of the ethoxylated alkylamine source, should preferably be higher than 90% to minimize the undesirable foam production during the bottling and manufacturing of the cleaning composition. Moreover, the content of AOEO and / or A1EO should preferably be less than 2% wt of the homolog blend, more preferably less than 1% to minimize the undesirable formation of foam during the manufacturing of the cleaning composition.

[0079] While this invention is susceptible of embodiment in many different forms, there is shown in the drawings and will herein be described in detail, a preferred embodiment with the understanding that the present disclosure should be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the embodiment so illustrated.

Claims

Claims1. A method of manufacturing a cleaning composition comprising an acid and an alkylamine ethoxylate comprising forming a mixture with a first amount of a blend of alkylamine ethoxylate comprising free alkylamine AOEO, alkylamine ethoxylates such as A1EO, and A2EO, hydrochloric acid, a quaternary ammonium compound (alkyl trimethyl ammonium chloride) and water until all ingredients are fully dissolved, wherein the combined content of free alkylamine and A1EO is less than 5%, preferably less than 3%, and further wherein the viscosity of the manufactured composition is at least 1500 cP at 20° C at 20 RPM Brookfield viscometer RV spindle 3.

2. The method according to claim 1 , further comprising mixing an alkyl phenol selected from the group consisting of a propylated phenol, a butylated phenol, a butylated hydroxyanisole, an amylated phenol, a hexylated phenol, a heptylated phenol or a combination thereof, and wherein a molar ratio of alkyl phenol to hydrochloric acid of between 0.75-1.5 of said alkyl phenol to 9 -25 of hydrochloric acid is obtained.

3. The method according to claim 1, further comprising adding a second amount of a blend of alkylamine ethoxylate to the mixture.

4. The method according to claim 3 further comprising allowing the mixture to traveling down at least one conduit into a bottle under a pressure ranging between 1.0 to 1.5 bar, preferably 1.2.

5. The method of claim 1, wherein the mixing is performed at temperature ranging between 30 to 75° C, preferably in the range of 45 to 65° C.

6. The method according to any of the prior claims, performed for a period of 90 to 300 minutes at temperatures ranging between 20 to 30° C.

7. The method of claim 2, wherein the molar ratio of alkyl phenol to hydrochloric acid is between 0.9-1.25 of said alkyl phenol to 12-22.5 of hydrochloric acid, preferably between 0.95- 1.15 of said alkyl phenol to 15-19 of said hydrochloric acid.

8. The method of claim 1, wherein the viscosity of the manufactured composition is in the range between 1650 to 3000 cP, preferably 1700 to 2250 cP at 20°C at 20 RPM Brookfield viscometer RV spindle 3.

9. The method of claim 1 , wherein the amount for the blend of alkyl amine ethoxylate ranges between 10 kg to 6000 kg, preferably between 50 kg to 3000 kg, more preferably between 75 kg to 1750 kg.

10. The method according to any of the prior claims wherein the alkyl phenol is 2- propylphenol, di propyl phenol, butylhydroxytoluene, dibutylhydroxytoluene, methylamylphenol, or any combinations thereof.

11. The method according to any of the prior claims, further comprising the step of measuring the content of AOEO and / or A1EO before adding the first or the second amount of said blend of alkylamine ethoxylate.

12. The method according to any of the prior claims, wherein the content of free alkylamine is less than 1%, preferably less than 0.5%, more preferably less than 0.1%.

13. The method according to any of the prior claims, wherein the content of the A1EO is less than 3%, preferably less than 2.5%, more preferably less than 1.5% and most preferably less than 0.4%.

14. A cleaning composition comprising: a. an acid at concentrations ranging between 0.5 to 30%, preferably 5 to 15%, b. a blend of alkylamine ethoxylate comprising free alkylamine, A1EO, and A2EO, wherein the combined content of free alkylamine ethoxylate and A1EO is less than 5%, preferably less than 3%, and c. an amount of quaternary ammonium, wherein viscosity of the composition is at least 1500 cP at 20 ° C at 20 RPM Brookfield viscometer RV spindle 3,20 rpm.

15. The cleaning composition of claim 14, wherein the acid is selected from the group consisting of hydrochloric acid, citric acid, sulfuric acid, formic acid, and any combinations thereof.

16. The cleaning composition of claim 14, wherein the composition comprises a butylated phenol, and wherein the molar ratio of the butylated phenol to acid in said composition is between 0.75-1.5 of said butylated phenol to 9 -25 of hydrochloric acid.

17. The cleaning composition of claims 14-16, wherein the content of free ethoxylate is less than 1%, preferably less than 0.5%, more preferably less than 0.1%.

18. The cleaning composition of claims 14-17, wherein the content of the A1EO is less than 3%, preferably less than 2.5%, more preferably less than 1.5% and most preferably less than 0.4%.

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