EP4608956A1

EP4608956A1 - Concentrated multipurpose hard surface cleaners

Info

Publication number: EP4608956A1
Application number: EP23798438.0A
Authority: EP
Inventors: Aleksandra BILINSKA-CHOMIK; Ewa Grzybowska; Monika PEKSA
Original assignee: Reckitt Benckiser Power Cleaners BV
Current assignee: Reckitt Benckiser Power Cleaners BV
Priority date: 2022-10-27
Filing date: 2023-10-26
Publication date: 2025-09-03
Also published as: GB202215921D0; AU2023366294A1; WO2024089214A1; GB2623945A

Abstract

Concentrated bathroom cleaning compositions containing at least one organic acid, at least one thickener, at least one non-ionic surfactant, and at least one auxiliary agent, wherein the composition having a viscosity ranging between 150 to 800 cP as measured under conditions: 20°C, Viscometer Brookfield LVDV, Spindle No. 2, at 50 rpm, for at least 12 weeks, 52 weeks, 112 weeks, preferably at least 240 weeks.

Description

CONCENTRATED MULTIPURPOSE HARD SURFACE CLEANERS

TECHNICAL FIELD

The present disclosure relates to concentrated multipurpose hard surface cleaners containing an organic acid, an alkyl glucoside, and a thickener.

BACKGROUND

There are a variety of hard surface cleaning compositions that have been described in the art. Such compositions are typically low viscosity ready to use combinations of a bleach material, surfactants, fragrances, and dyes producing their desired aesthetic, cleaning, disinfecting, or deodorizing effects. Concentrated formulations are rare due to their corrosive and undesirable safety profile.

As the industry is moving towards environmental friendlier formulations and sustainable solutions, there is a need for concentrated non-corrosive cleaner compositions that can provide such unmet need for consumers. The invention described herein below addresses such short comings in the art.

SUMMARY OF THE INVENTION

The present invention can be characterized as an instrument of change in consumer's pattern of use towards environmentally friendlier and sustainable options. The present invention provides concentrated non-corrosive hard surface cleaning compositions that can be used as a refill stock for generating a diluted ready to use cleaning composition for hard surfaces. In addition, the present invention contains less amount of plastic and paper for packaging giving the consumers an option to reuse the respective dispensing containers.

In the first aspect of the present invention is directed to concentrated bathroom cleaning compositions that contains at least one organic acid, at least one thickener, at least one non-ionic surfactant, and at least one auxiliary agent, wherein the composition having a viscosity ranging between 150 to 800 cP as measured under conditions: 20 °C, Viscometer Brookfield LVDV, Spindle No. 2, at 50 rpm, expressed in cP or centipoise or milli-pascal per second (1 cP = 1 mPa-s), for at least 12 weeks, 52 weeks, 112 weeks, preferably at least 240 weeks. In some embodiments, the concentrated compositions have a pH ranging between 2.0 to 4.0 at room temperature, and a density ranging between 1.1 to 1.4 g/ml at 20°C. In some embodiments, the composition is substantially free of any anionic, cationic and/or amphoteric surfactants. In some embodiments, the non-ionic surfactant is the sole source of a surfactant, and the composition is free of any anionic, cationic and/or amphoteric surfactants.

In some embodiments, the concentrated compositions according to the present invention exhibit continuous stability for at least 12 weeks, 18 weeks, 26 weeks, 52 weeks, 104 weeks, 112 weeks, 156 and 240 weeks at room temperature of 25° C and 30 ° C 65%RH with less than 5% variation in their viscosity, pH, density, appearance, color and/or odor.

In some embodiments of the first aspect of the invention, the organic acid may be citric acid, acetic acid, lactic acid, formic acid, oxalic acid, uric acid, malic acid, sorbic acid and glycolic acid. In preferred embodiments, the organic acid is citric and glycolic acids with citric acid being the most preferred acid. In some embodiments, the concentration of the organic acid in the compositions according to the present invention ranges between about 2.5% w/w to about 45% w/w, preferably between about 5% to about 42.5% w/w, most preferably between 20% w/w to 40% w/w.

In some embodiments the thickener is a gum based thickener. In some embodiments, the gum-based thickener is selected from the group consisting of xanthan, alginic, guar gum, locust bean gum, diutin, carrageenan, arabic and acacia gum. Particularly preferred is xanthan gum (CAS# 11138-66-2). In some embodiments the thickeners are present in amounts ranging between 0.01% w/w to about 1% w/w, preferably in the range of 0.07 to about 0.5% w/w. In some embodiment, the gum based thickener has a molecular weight ranging between 5,000 to about 5,000,000 daltons. In some embodiments, the gum based thickener is xanthan gum and the xanthan gum is the sole thickener of the composition

In some embodiments, the non-ionic surfactant may be an alkyl polyglucoside C6-C16 alkyl polyglucoside, preferably C8-C10 alkyl polyglucoside. In some embodiments, the alkyl polyglucoside may be at least one of the following: decyl glucoside, capryl/caprylyl glucoside, myristyl glucoside, coco glucoside, caprylyl/myristyl glucoside and lauryl glucoside. More preferred of the alkyl polyglucosides is caprylyl/capryl glucoside and caprylyl/myristyl glucoside. In some embodiments, the concentration of the alkyl polyglucoside may range between about 0.5 w/w to about 7% w/w, preferably between 0.5% w/w to about 5% w/w.

In second aspect of the invention, the compositions is a concentrated non-corrosive aqueous composition comprising (a) about 5% to about 40% w/w of citric acid; (b) about 0.02% to 0.5% by w/w of a thickener; (c) about 0.5% to 5.0% w/w of C8-C10 alkyl polyglucoside; nonionic surfactant; (d) about 0.02% to 0.35 % by weight of a soil-repelling polymer. In other embodiments, the composition may further contain water, trisodium citrate, sodium hydroxide. In some embodiments, the amount of water may range between 45 to 95% by weight. In a preferred embodiment, the amount of water ranges between about 45% to about 55% by weight. In some embodiments, the composition is free of any other cationic, anionic or amphoteric surfactants. In some embodiments, the composition is a homogenous composition having no lumps after at least 52 weeks storage at the room temperature.

In some embodiments, the composition according to the present invention consists essentially of: (a) from 30% to 50% w/w of citric acid, preferably 33.5% to 40% (b) from 0.15% to 0.25% w/w of xanthan gum, (c) from 3.5% to 4.5% w/w of C8-C10 alkyl polyglucoside, (d) from 0.20% to 0.30% of modified starch polymer as the soil-repelling polymer, (e) from 4.5% to 5.5% w/w sodium hydroxide, and optionally a perfume or a dye ingredient, wherein the composition has a viscosity ranging between 150 to 800 cP.

In third aspect, the present invention provides for methods of cleaning hard surfaces by further and applying the diluted composition to the hard surfaces of interest.

In fourth aspect, the present invention is directed to methods of manufacturing a hygienic composition in a container comprising the steps of placing the concentrated compositions according to the first aspect of the present invention to a container and diluting the concentrated composition by adding water to the container and mixing the resulting composition. In another aspect, the present invention provides for methods of cleaning hard surfaces in bathrooms such as toilet bowls, bathroom tiles and floors or the like by applying the cleaning composition according to the fourth aspect of the present invention. In some embodiments, the method further includes the step of applying water to remove undesirable scaling and odor in the area of interest.

DETAILED DESCRIPTION OF THE INVENTION

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 (e.g., hydrate), protected forms, and other stereoisomers thereof, isomeric forms, including racemic and other mixtures thereof.

As used herein, "about" will mean up to plus or minus 5% of the particular term.

As used herein, "consisting essentially of" refers to excluding other active ingredients but including the recited optional excipients. As used herein, "consist of" or "consisting of" refers to compositions that only includes the recited ingredients.

By the term "substantially free" it is meant that the final composition 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 composition or if detected, but less than 1% of the total weight of the respective composition only in the form of residual content of the ingredient or the composition containing such ingredient. For example, the phrase substantially free of amphoteric surfactant would mean that the respective composition contains less than 1% of any amphoteric surfactant. On the other hand, the phrase "free of" reflects that the claim is free of any traces of the ingredient at issue.

As used herein, the term "viscosity" refers to the dynamic viscosity, as measured using a Brookfield viscometer (spindle no. 2, at 50 rpm, at 20°C). As used herein, the term "continuous stability" refers to the type of stability wherein the composition at issue does not exhibit any phase separation at the specifically recited temperatures and humidity for the specific duration of time, and further exhibit less than 10% variation in its original content of ingredients, or the respective viscosity, pH, density, appearance, color or odor characteristics.

All ranges described herein are meant to be inclusive of all amounts therebetween. For example, a range of dispersant system from 40% to 45% by weight is intended to cover all amounts or concentrations therebetween including 40%, 41%, 42%, 43%, 44% and 45% by weight.

The present inventors have discovered combinations of organic acids, thickeners, nonionic surfactants, providing a concentrated non-corrosive hard surface cleaning compositions that achieve enhanced hygienic activities and sanitation when applied to hard surface areas of the bathroom. Accordingly, the first aspect of the present invention is an unique combinations of at least one organic acid, at least one thickener, at least one non-ionic surfactant, and at least one auxiliary agent, wherein the composition having a viscosity ranging between 100 to 800 cP as measured under conditions: 20°C, Viscometer Brookfield LVDV, Spindle No. 2, at 50 rpm, expressed in cP or centipoise or milli-pascal per second (1 cP = 1 mPa-s) for at least 12 weeks, 52 weeks, 112 weeks, preferably for at least 240 weeks.

In some embodiments, the concentrated compositions have a pH ranging between 2.0 to 4.0 at room temperature, and a density ranging between 1.1 to 1.4 g/ml at 20°C. In some embodiments, the composition is substantially free of any anionic, cationic and/or amphoteric surfactants. In some embodiments, the non-ionic surfactant is the sole source of a surfactant and the composition is free of any anionic, cationic and/or amphoteric surfactants.

In some embodiments, the concentrated compositions according to the present invention exhibit continuous stability for at least 12 weeks, 18 weeks, 26 weeks, 52 weeks, 104 weeks, 112 weeks, 156 and 240 weeks at room temperature of 25° C and 30 ° C 65%RH with less than 10% variation, preferably less than 5% variation in their ingredient content, viscosity, pH, density, appearance, color and/or odor. In some embodiments, the concentrated compositions according to the present invention exhibit continuous stability for at least 3 weeks, 6 weeks, 12 weeks, or 18 weeks, in extreme conditions, wherein temperature may range 60° C to -10° C, humidity is at least 40 ° C 75%RH, and the composition exhibits less than 10% variation, preferably less than 5% variation in their original ingredient content, viscosity, pH, density, appearance, color and/or odor.

In second aspect of the invention, the compositions is a concentrated non-corrosive aqueous composition comprising (a) about 5% to about 40% w/w of citric acid; (b) about 0.02% to 0.5% by w/w of a thickener; and (c) about 0.5% to 5.0% w/w of C8-C10 alkyl polyglucoside as the non-ionic surfactant. In some embodiments, the thickener is xanthan gum ranging between about 0.17 to 0.35 % by weight of the composition. In other embodiments, the composition may further contain water, trisodium citrate, sodium hydroxide.

In some embodiments, the amount of water may range between 45 to 95% by weight. In a preferred embodiment, the amount of water ranges between about 45% to about 55% by weight. In some embodiments, the composition is free of any other cationic, anionic or amphoteric surfactants. In some embodiments, the composition is a homogenous composition having no lumps after at least 52 weeks storage at the room temperature.

In some embodiments, the concentrated non-corrosive aqueous composition of the present invention contains (a) about 30% to about 50% w/w citric acid, (b) about 0.1% to about 0.3% w/w xanthan gum, (c) about 3% to about 5% w/w of C8-C10 alkyl polyglucoside, (d) about 0.15% to about 0.35% modified starch polymer, (e) about 3% to about 6% w/w sodium hydroxide, and optionally a perfume or a dye ingredient.

In some embodiments, the concentrated composition according to the present invention consists essentially of: (a) from 33.5% to 40% w/w of citric acid, (b) from 0.15% to 0.25% w/w of xanthan gum, (c) from 3.5% to 4.5% w/w of C8-C10 alkyl polyglucoside, (d) from 0.2% to 0.3% of modified starch polymer, (e) from 4.5% to 5.5% w/w sodium hydroxide, and optionally a perfume or a dye ingredient, wherein the composition has a viscosity ranging between 150 to 800 cP and a pH ranging between 2 to 4. In another embodiment, such concentrated composition may further be diluted with water to form a ready to use formula. In other embodiment, the concentrated composition consists of (a) about 33.5% to about 40% w/w citric acid, (b) about 0.15% to about 0.25% w/w xanthan gum, (c) about 3.5% to about 4.5% w/w of C8-C10 alkyl polyglucoside, (d) about 0.2% to about 0.3% modified starch polymer, (e ) about 4.5% to about 5.5% w/w sodium hydroxide, and a perfume or a dye ingredient. In another embodiment, such concentrated composition may further be diluted with water to form a ready to use formula.

In some embodiments, the concentrated composition is diluted with suitable amount of a solvent to form a ready to use composition containing: ( a) from 4.5% to 7.5% w/w of citric acid, (b) from 0.020% to 0.045% w/w of xanthan gum, (c) from 0.5% to 1.5% w/w of C8-C10 alkyl polyglucoside, (d) from 0.02% to 0.05% of modified starch polymer, (e ) from 0.5% to 1.5% w/w trisodium citrate, and optionally a perfume or a dye ingredient, wherein the composition has a viscosity ranging between 2 to 10 cP and a pH ranging between 2 to 4. In some embodiments, such ready to use diluted composition is substantially free of sodium hydroxide.

In preferred embodiments, the ready to use diluted composition consists essentially of (a) from 5% to 6.5% w/w of citric acid, (b) from 0.025% to 0.035% w/w of xanthan gum, (c) from 0.5% to 1.5% w/w of C8-C10 alkyl polyglucoside, (d) from 0.02% to 0.05% of modified starch polymer, (e ) from 0.75% to 1.0% w/w trisodium citrate, and optionally a perfume or a dye ingredient, wherein the composition has a viscosity ranging between 2 to 6 cP and a pH ranging between 2 to 4. In more preferred embodiments, such ready to use diluted composition is free of sodium hydroxide.

In some embodiments, the ready to use diluted compositions according to the present invention exhibit continuous stability for at least 12 weeks, 18 weeks, 26 weeks, 52 weeks, 104 weeks, 112 weeks, 156 and 240 weeks at room temperature of 25° C and a humidity of 30 ° C 65%RH , wherein the composition exhibits less than 10%, preferably less than 5% variation in their original ingredient content, viscosity, pH, density, appearance, color and/or odor. In some embodiments, the ready to use diluted compositions according to the present invention exhibit continuous stability for at least 3 weeks, 6 weeks, 12 weeks, or 18 weeks, in extreme conditions, wherein temperature may range 60° C to -10° C, humidity is at least 40 ° C 75%RH, and the composition exhibits less than 10% variation, preferably less than 5% variation in their original ingredient content, viscosity, pH, density, appearance, color and/or odor.

For the sake of clarity, any disclosed ranges provided herein include all ranges and values therebetween. Thus, for example a viscosity that ranges between 150 to 800 cP, includes all values and ranges therebetween including 151, 180, 190, 215, 230, 240, 250, 270, 280, 350, 375, 450, 500, 550, 600, 650, 700, 750, and so on.

In some embodiments, the composition of the present invention further contains a biocidal agent, fragrance, a dye, a binder, a bittering agent, acidity regulators, pH adjustor, a chelating agent, anti-caking agents, suitable fillers, or any mixtures thereof. In some embodiments, the composition is a solid lavatory cleaning composition containing a dispersant, a thickener, a non-ionic surfactant, a biocide material and a fragrance. In some embodiments, the biocide agent may be a single quaternary ammonium or a combination of quaternary ammonium material that provides germicidal activities.

Organic Acids

The organic acid according to the present invention are preferably those that are not corrosive at concentration that can provide sufficient cleaning properties. Accordingly, the organic acids of choice are citric acid, acetic acid, lactic acid, formic acid, oxalic acid, uric acid, malic acid, sorbic acid glycolic acid and any combinations thereof at such concentrations that do not corrosive. In preferred embodiments, the organic acid is citric and glycolic acids with citric acid being the most preferred acid. Suitable concentration of the organic acid in the compositions according to the present invention ranges between about 4.5% w/w to about 75% w/w; between about 5% to about 50% w/w; between about 30% to about 50%; between 35% to 45%; but preferably between 37.5% w/w to 40% w/w. In one embodiment, the pH of the concentrated composition is in the range of 2.0-4.0, preferably above 2.0 but less than 3.5.

In most preferred embodiments, the concentrated compositions according to the present invention contains about 30% to about 50% w/w of the organic acid. If citric acid is used, the preferred concentrations of the citric acid in the final concentrated formulation is between 35% w/w to about 45% w/w. In other embodiments, the concentrated compositions may be diluted with additional water, or other aqueous solvents up to 500, 650, 750, 1000, 1500 or 2000 ml of such solvents. In such cases, the preferred concentration of the citric acid may range between 5% to about 7.5% w/w.

Thickeners

In certain aspects of the present invention, the inventors have discovered that use of any thickener may not provide the suitable viscosity and stability for the intended purposes of the presently describe non-corrosive concentrated compositions. Proper thickeners according to the present invention are those that would provide suitable viscosity for dispensing through a trigger system, at a concentrations level below 2% w/w, preferably at a concentrations level below 1% w/w, and more preferably at concentration level below 0.5%. To that end, the inventors have discovered that only a selected group of thickeners can provide the desired viscosity and stability. Optimal level of the viscosity of the liquid composition according to the present invention may range from 100 to 800 cP, or from 125 to 500 cP, and preferably between 150 cP to 300 cP, at 20° C as measured with Brookfield Viscometer Brookfield LVDV, Spindle No. 2, at 50 rpm as specified.

In some embodiments, the compositions of the present invention contain a gum-based thickener selected from the group consisting of a xanthan, alginic, guar gum, hydroxypropyl guar gum, locust bean gum, diutin, carrageenan, arabic and acacia gum or any combinations thereof. In preferred embodiments, the thickener is a single gum-based thickener that is not a cellulose based thickener. In most preferred embodiments, the thickener is free of any cellulose or cellulose derivatives such as hydroxyethyl cellulose, hydroxy methyl cellulose, hydroxypropyl cellulose. In some embodiments, the sole thickener is xanthan gum and the composition is free of any other gum based thickener.

In some embodiments, the composition can further contain a second thickener such methyl cellulose, crystalline cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, methyl vinyl ether/maleic anhydride copolymer, dimethyl polysiloxane, sodium starch glycolate, sodium starch phosphate ester, sodium polyacrylate, carboxymethyl guar gum, methyl cellulose, crystalline cellulose, polyvinylpyrrolidone, polyvinyl alcohol (PVA), clay materials, acid derivatives, acid copolymers, urethane associate thickeners (UAT), polyether urea polyurethanes (PEUPU), polyether polyurethanes (PEPU), or an inorganic thickener such as sodium magnesium silicate, lithium magnesium sodium silicate, acrylic acid/behenic acid copolymer, calcium carbonate, calcium silicate, magnesium silicate, silica powders, various glasses, amorphous hydrated silicic acid or fumed silica.

In certain embodiments, the gum based thickener may have a molecular weight ranging from 50,000 to about 5,000,000; 75,000, to 4,000,000; preferably between 100,000 to 2,500,000 and more preferably between 1,000,000 to 2,000,000 g/mol (or 1 and 2 million Daltons). In certain embodiment, the gum-based thickener has a viscosity ranging between 1000- 3500 for 1% solution when measured at 25°C after 2 hours with Brookfield viscometer, LVDV, #3 spindle at 60 RPM.

In some embodiments, the thickeners is xanthan gum in amounts ranging between 0.01% w/w to 2% w/w, preferably in the range of 0.07 to 0.5% w/w. In some embodiments, the xanthan gum in the concentrated composition according to the present invention is present in amount ranging between about 0.15 to about 0.25 % w/w. In other embodiments, the ratio between the gum-based ingredient and the organic acid is in the range of 1:150 respectively to about 1:250, preferably in the range of 1:175 to about 1: 195. In certain embodiments, wherein the thickener is xanthan gum and the organic acid is citric acid, the ratio between xanthan gum to citric acid can range between 1:175 to 1:195.

Surfactants

The non-ionic surfactant used in the present invention is preferably an alkylpolyglucoside. Suitable alkyl polyglucosides include C6-C16 alkyl polyglucoside, preferably C8-C10 alkyl polyglucoside. In some embodiments, the alkyl polyglucoside may be at least one of the following: decyl glucoside, capryl/caprylyl glucoside, myristyl glucoside, coco glucoside, caprylyl/myristyl glucoside and lauryl glucoside. More preferred of the alkyl polyglucosides is caprylyl/capryl glucoside, octyl/decyl/glucoside, caprylyl/myristyl glucoside or any combinations thereof. In some embodiments, the concentration of the alkyl polyglucoside may range between about 0.5 w/w to about 7% w/w, preferably between 0.5% w/w to about 5% w/w. In preferred embodiments, the non-corrosive concentrated composition contains about 3% to about 5% w/w of C8-C10 alkyl polyglucoside. In more preferred embodiment, the non-corrosive concentrated composition according to the present invention contains about 3.5% to about 4.5% w/w of C8-C10 alkyl polyglucoside.

Other non-ionic surfactant that may be used include a great variety of alkoxylated alcohols, especially ethoxylated and/or propoxylated alcohols, is conveniently commercially available. , preferred alkoxylated alcohols for use herein are nonionic surfactants according to the formula RO(E)e(P)pH where R is a hydrocarbon chain of from 2 to 24 carbon atoms, E is ethylene oxide and P is propylene oxide, and e and p which represent the average degree of, respectively ethoxylation and propoxylation, are of from 0 to 24 (with the sum of e+p being at least 1). Preferably, the hydrophobic moiety of the nonionic compound can be a primary or secondary, straight or branched alcohol having from 8 to 24 carbon atoms. Such suitable nonionic surfactants are commercially available under such trade names as Pluronics® or Lutensol®.

Biocide material

The presence of biocidal material in the compositions according to the invention is optional. In certain embodiments, the compositions of the present invention contain a biocide such as any one or more of the antivirals, antimicrobials, antibacterials, antifungals, antiprotozoals, antiarcheals, and/or antiparasitic that is selected from quaternary ammonium- based biocides. Examples of such quaternary ammonium biocides are n-alkyl dimethyl benzyl ammonium chloride, n-alkyl, dimethyl ethyl benyl ammonium chloride, dodecyl dimethyl ammonium chlorides (DDAC), cetyl trimethyl ammonium chloride (CTAC), benzalkonium chloride (BAC), or any mixtures thereof. In certain embodiments, the biocide material includes n-alkyl dimethyl benzyl ammonium chloride, n-alkyl, dimethyl ethyl benyl ammonium chloride, either alone or in combination together as provided under the BTC® 2125M series by Stepan. In some embodiments, the quaternary ammonium biocide having at least one alkyl chain having a length of C12-C18, more preferably a mixture of C12-C14, with concentration of C12 ranging between 5% to about 70% by weight, and concentrations of C14 ranging between 30- 70% by weight, preferably between 60-68% by weight or any combinations thereof.

Optional Auxiliary Ingredients

In some embodiments, the present composition may include one or more additional optional ingredients selected from the group consisting of soil-repelling polymers, dye, a fragrance, a chelating agent, preservatives, bitterness flavorant, radical scavengers, hydrotropes, anticorrosion agents, opacifiers, brighteners, abrasives such as silica, kaolin, talc or an absorbent.

Soil-repelling polymers are those polymers that reduce soil adhesion on hard surfaces by generally leaving a polymeric film on hard surfaces and enhancing surface shine. They include amphoteric modified starch polymers or the like that are capable of boosting shining effects, providing long lasting cleaning, glossy effect by hydrophilizing hard surfaces and reducing soil adhesion on such surfaces. Suitable starch polymers are plant-based amphoteric modified, such as bio-based polymers commercially available as Polyquart® Ecoclean Max A by BASF. In some embodiments, the modified starch polymer may be used at from 0.02% to 0.35% w/w, preferably between 0.15% to 0.30% and most preferably at 0.25% w/w. Other suitable soil-repelling polymers include PVP (polyvinylpyrrolidone) commercially available as Sorez hs 205 ® from ISP Freetown Fine Chemicals Inc. In some embodiments, the suitable soil-repelling polymer is PVP.

Suitable dyes 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), Duasyn Acid Blue AE 03 or the like.

Suitable fragrances that may be used in this invention includes natural or synthetic fragrances inducing 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.

Methods of manufacturing and use of the Composition

In other aspects, the present invention provides for methods of manufacture a hygienic composition comprising the steps of manufacturing the concentrated composition by mixing the ingredients by methods known in the art to a viscosity ranging from 100 to 800 cP, or from 125 to 500 cP, and preferably between 150 cP to 300 cP. In some embodiments, the concentrated composition is subsequently diluted with sufficient water to reach an organic acid level ranging between 4 to 8 w/w in the resulting composition, preferably at a temperature ranging between 20° C to 25 °C, and shaking the resulting composition to assume a viscosity ranging from 2 to 10 cP at 20° C to 25 ° as measured by the process described therein above.

In some embodiments, the concentrated composition according to the present invention can achieve a shelf life of at least 12 weeks, 52 weeks, 112 weeks, preferably at least 240 weeks, a viscosity ranging from 100 to 800 cP, or from 125 to 500 cP, and preferably between 150 cP to 300 cP. Furthermore, the concentrated compositions according to the present invention exhibit continuous stability for at least 12 weeks, 18 weeks, 26 weeks, 52 weeks, 104 weeks, 112 weeks, 156 and 240 weeks at room temperature of 25° C and 30 ° C 65%RH with less than 10%, preferably less than 5% variation in their viscosity, pH, density, appearance, color and/or odor from its original content.

In some embodiments, the diluted liquid aqueous cleaning composition derived from the concentrated composition may contain (a) from about 4.00% to about 7.5% by weight of the organic acid; (b) from about 0.015% to about 0.04% by weight of a thickener; (c) from about 0.30% to about 0.75% by weight of a non-ionic surfactant; and (d) from about 85% to about 95% by weight of a water, wherein the diluted liquid aqueous composition having a viscosity ranging from 2 cP to 10 cP at 20°C as measured using spindle 2 at 50 rpm on a Brookfield viscometer. In some embodiments, the viscosity of the diluted liquid aqueous composition ranges between 3 to 5.5. In some embodiments, the liquid composition further contains a dye, a fragrance and a pH modifier.

In another aspect, the present invention provides for methods of cleaning hard surfaces in bathrooms such as toilet bowls, urinal, lavatory fixtures, bathroom, showers, washbasin/sink, bathroom fittings (shower head, faucets) and flooring tiles and floors by mixing the concentrated liquid composition according to the present invention, in a container diluting the composition with water to reach 750 ml, and applying the resulting cleaning composition to the area of interest and optionally applying water to remove undesirable scaling and odor in the same area.

Hard surfaces according to this invention include such material as bricks, ceramic, cement, crystal, diamond, glass, latex, marble, metallic (preferably non-copper or non-brass), pebbles, porcelain, polymeric and quarry tiles, and natural stone. By way of example, hard surfaces are preferably non-porous hard surfaces and may include surfaces composed of plastic such as PMMA plates, molten polycarbonate, foamy PVCs glazed, polyester, vinyl; vinyl floorings such as Polyflors, including Polyflor oatmeal 9240 yellow, Polyflor Frosted Mint PC2, Polyflor Gray; metals such as stainless steel, Aluminum; Counter Tops such as laminated MDF; Tiles such as refrigerator top, baked enamel, ceramic bathroom shiny tiles, ceramic bathroom matt ties, terra cotte, tempered glass, mirror; Floor panels, such as Ash, Oak or Bamboo floor panels; bathroom fittings particularly chrome bathroom fittings and fiberglass, Formica™, Corian™ or lavatory fixtures; and other hard surfaces known to the industry.

In some embodiments, the concentrated compositions according to the present invention are manufactured by first adding water into a mixing tank at temperatures ranging between 22 °C-25 °C. Low water temperature prolongs the time needed to dissolve the ingredients. The mixer is subsequently turned on and set at moderate speed to avoid foaming. In the next step, the gum-based thickener such as xanthan gum is added and mix until dissolved followed by adding the organic acid (i.e. Citric acid) to form a uniform solution. NaOH is then added slowly formula while controlling temperature and mix for 5 min. In the next step, the Alkylpolyglucoside is added and mixed for next 5 min or until uniform. In the next step, soilrepelling polymers such as derivatized starch polymer is added and mixed for next 5 min or until uniform followed by the perfume. The entire mixture is mixed for 15minutes until product is completely homogenous. The concentrated composition may further be diluted with water to prepare the ready to use formula.

Examples

The foregoing examples include descriptions of preferred embodiments of the first aspect of the present invention in concentrate form and the resulting diluted composition forming a homogenous aqueous liquid composition having a viscosity of ranging 3 to 5.5 cP.

Table 1 below provides the components and the preferred ranges of the concentrated composition according to the present invention as well as the diluted ready to use version at pH ranging 2.5 to 4. The concentrated composition were manufactured according to the process steps set forth above and then diluted in 750 ml with water to prepare the ready to use composition having a viscosity ranging between 3 to 5.5 cP.

Table 1 a- Trisodium citrate was formed after the addition of the citric acid anhydrous into the solvent and allowing citric acid to react with NaOH in the mixture. The concentration of the respective ingredients where measured in the concentrated composition. b- Modified starch polymer used in this example was Polyquart® Ecoclean Max A by BASF

The inventors further compared various thickeners and their performance against each other when combined with citric acid, polyglucoside and the modified starch polymer. The list of the thickeners used in these examples are identified in Table 2 below all of which are commercially available by various suppliers:

Table 2

Table 3 provides the composition according to the present invention in Example 1, and various comparative examples. The compositions of Table 3 were formulated according to the process steps described above, except that Examples 2-10 differ in the type and content of the thickener used. It was surprisingly observed that composition of the Examples 2-10 are inferior as compared to the composition of Example 1 by failing to meet various feasibility criteria.

Table 3 a- Measured post reaction after the addition of citric acid anhydrous into the mixture. NaOH amounts will be reduced after the reaction towards zero. b- Measured within the first 3 weeks, under conditions: 20 °C, Viscometer Brookfield LVDV, Spindle No.

2, at 50 rpm. c- By "Failed" it is meant that the formula failed the feasibility criteria for various reasons including but not limited to proper viscosity, poor cleaning performance, failure to flow through trigger system and non-homogeneity. Only Example 1 met all such criteria.

Table 3 further shows superiority of the gum based thickeners according to the present invention as compared to various other thickeners. Example 1 was the only combination that provided superior viscosity, shelf-life stability while meeting the feasibility criteria. The composition of Example 1 was then diluted up to 750 ml. The cleaning effectiveness of the diluted composition was tested based on IKW (Industrieverband Koerperpflege und Waschmittel e.v) Recommendations for the Quality Assessment of Bathroom Cleaners section, and Determination of limescale removal properties by marble slab immersion in ready to use bathroom cleaner, under following conditions: 1) 10s soaking time, 10 min exposure in vertical position

2) 5s soaking time, 10 min exposure in vertical position

3) lOmin soaking time in horizontal position

Table 4 provides the results of the effectiveness of the diluted compositions according to the present invention.

Table 4

The composition of Example 1 of the present invention was subsequently tested against other prior art formulations, namely Examples 16 and 20 of US 2011/0028369 (respectively Test Compositions A and B), Example 21 of WO 2022/175661 (Test Composition C), and Example El of GB 2341870 (Test Composition D) for their ability to remove limescale respectively according to the following process steps set forth below. Each of the Test Compositions A, B, C and D were made according to the directions provided in the respective prior art document. To enable direct comparability among the compositions, all test compositions were diluted in a corresponding manner. Accordingly, each of the liquid composition (Test Compositions A, B, D and Example 1 of the present invention) were diluted at the ratio of 100 ml of the respective composition with 650 ml of water to reach the total of 750ml. The powder formulation (Test Composition C) was diluted at the concentration of 25grams of powder with 650 ml of water.

The test slabs were prepared by obtaining Carrara marble sized 75x150x5mm (each slab shall only be used for one experiment). Prior to testing marble slabs were degreased with ethanol. Any residues were removed under running water with a brush. The slabs were dried at 105°C for at least lh to constant weight. After cooling down the slabs were weighted out on an analytical balance (precision +/-lmg).

To conduct the horizontal surface test, a 250ml of the cleaner formulation was transferred to a suitable cuvette (to assure full immersing of slab in the product). Then a test slab was totally immersed for 5 minutes in the cleaner. The treated marble slabs were then rinsed under running water and any adhering residues were brushed off, followed again by drying at 105°C to constant weight and weighting. The quantity of dissolved calcium carbonate (limescale) is determined by the difference in weight of the slabs before and after. The determination of the descaling power of each product was carried out using 5 marble slabs and always using fresh cleaning solution. (Table 5)

To conduct the vertical surfaces test, a 250ml of the cleaner was transferred to a suitable cuvette. Then a test slab was totally immersed for 10 sec in the cleaner. As the next step, the test slab was immediately removed and placed vertically in a stand intended for this purpose to ensure that the product can run off without forming a pool at the base of the marble slab. Exposure time in the vertical position was 5 minutes. After that the test slab is rinsed for 30 seconds under running water before the slab is once again immersed in the cleaner formulations. (Table 6) Three immersion cycles were carried out, each with fresh cleaner formulations. The treated marble slab is then rinsed under running water and the adhering residues were brushed off, followed again by drying at 105° C to constant weight and weighting. The quantity of dissolved calcium carbonate (limescale) is determined by the difference in weight.

The determination of the descaling power of each product was carried out using 5 marble slabs as reflected in the before and after columns and results in Tables 5 and 6 below.

Table 5- Limescale removal - horizontal

Test conditions: soaking time- 5 min Table 6- Limescale removal - vertical soaking time -10 s

3 cycles

Test conditions: exposure time- 5 min

In both vertical and horizontal testing, the average reduction in weight is much higher for formulation that is made according to the present invention, i.e. Example 1, as opposed to those of the prior art of Test Compositions A-D. As such, it is observed that the limescale removal of the formulations according to the present invention is far superior to the closest comparable formulations described in prior art. While multiple embodiments are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the detailed description and examples are to be regarded as illustrative in nature and not restrictive.

Claims

1. An aqueous cleaning compositions comprising at least one non-ionic surfactant, at least one organic acid, at least one gum based thickener, and at least one auxiliary agent, wherein the composition has a viscosity ranging between 150 to 800 cP as measured under conditions: 20 °C, Viscometer Brookfield LVDV, Spindle No. 2, at 50 rpm, expressed in cP or centipoise or milli-pascal per second (1 cP = 1 mPa-s), for at least 12 weeks, 52 weeks, 112 weeks, preferably at least 240 weeks.

2. The composition according to claim 1, wherein: a. the nonionic surfactant is selected from the group consisting of alkylpolyglucosides in an amount ranging between 0.5 w/w to about 7% w/w, preferably between 0.5% w/w to about 5% w/w; b. the organic acid is present in amount ranging between 4.5% to 75% by weight of the composition, preferably between 30% w/w to 50% w/w, and most preferably between 33.5% w/w to 40% w/w; and c. the thickener is gum based and is present in amount ranging between 0.01% w/w to about 2% w/w, preferably in the range of 0.07 to about 0.5% w/w.

3. The composition according to any one of the prior claims, wherein the at least one nonionic surfactant is the sole source of the surfactant.

4. The composition according to any one of the prior claims, wherein the at least one nonionic surfactant is selected from the group consisting of C6-C16 alkyl polyglucoside, preferably C8-C10 alkyl polyglucoside.

5. The composition according to any one of the prior claims, wherein the nonionic surfactant is C8-C10 alkyl polyglucoside, preferably in the range about 3 to about 5% w/w of the composition.

6. The composition according to any one of the prior claims, wherein the composition further contains a soil-repelling polymer selected from the group consisting of modified starch polymer or PVP, in an amount of 0.02% to 0.35% w/w, preferably between 0.15% to 0.25% and most preferably at 0.25%.

7. The composition according to any one of the prior claims, further comprising water in an amount of 45% w/w to 95% w/w.

8. The composition according to any of the prior claims, wherein a pH level of the composition is between 2 to 4.

9. The composition according to any of the prior claims, wherein the organic acid is selected from the group consisting of citric acid, lactic acid, oxalic acid, uric acid, malic acid, sorbic acid and glycolic acid.

10. The composition according to any of the prior claims, wherein the gum based thickener is xanthan gum and the xanthan gum is the sole thickener of the composition.

11. The composition according to anyone of the prior claims, wherein the organic acid is citric acid and the thickener is xanthan gum.

12. The composition according to anyone of the prior claims, wherein the ratio between the gum-based thickener and the organic acid is in the range of 1:150 to 1:250, preferably in the range of 1:175 to 1: 195 based on weight ratios.

13. The composition according to any one of the prior claims, wherein the composition consists essentially of: (a) from 30% to 50% w/w, preferably 33.5% to 45% w/w of citric acid (b) from 0.15% to 0.25% w/w of xanthan gum, (c) from 3.5% to 4.5% w/w of C8-C10 alkyl polyglucoside, (d) from 0.2% to 0.3% of modified starch polymer, (e ) from 4.5% to 5.5% w/w sodium hydroxide, and optionally a perfume or a dye ingredient, wherein the composition has a viscosity ranging between 150 to 800 cP.

14. A method of cleaning a hard surface, wherein the composition according to any of the prior claims is diluted with water for cleaning purposes and then applied to a hard surface area of interest.