WO2015171092A2

WO2015171092A2 - Use of oxidized humic acid its salts and derivatives in hard surface cleaning compositions

Info

Publication number: WO2015171092A2
Application number: PCT/TR2015/000177
Authority: WO
Inventors: Fikret Koc; Ahmet Ergun; Deniz YILMAZ; Serdar Soylemez
Original assignee: Hayat Kimya Sanayi Anonim Sirketi
Priority date: 2014-05-07
Filing date: 2015-04-29
Publication date: 2015-11-12
Also published as: EP2987846A1; WO2015171092A3

Abstract

The present invention relates to the field of hard surface compositions. In particular this invention relates to the use of oxidized humic acid compounds, its salts and derivatives or its mixtures, in hard surface cleaning compositions. This effective builder is useful for enhancement of cleaning capacity. Cleaning compositions of the present invention are prepared by using oxidized humic acid,its salts and derivatives or mixtures thereof and used for cleaning purposes glass, metal, plastic, ceramic, stone, tile, floor, sink, wash basin, toilet bowl, bathtube, bathroom, kitchen bench, building facade and similar surfaces.

Description

USE OF OXIDIZED HUMIC ACID ITS SALTS AND DERIVATIVES IN HARD SURFACE CLEANING COMPOSITIONS

DESCRIPTION

FIELD OF THE INVENTION

This application relates to hard surface cleaning compositions.

Particularly this application relates to the use of oxidized humic acid, its salts, its derivatives and mixtures thereof in hard surface cleaning compositions. This application relates to the hard surface cleaning compositions whereas oxidized humic acid, its salts, its derivatives and mixtures thereof is added to the composition in situ after synthesis or after separation of oxidized humic acid from reaction mixture.

This application relates to the synthesis of oxidized humic acid which is compatible for the use in hard surface cleaning compositions.

BACKGROUND OF THE INVENTION

Hereinafter in the text the synonym "oxidized humic acid" will be standing for "oxidized humic acid, its salts, its derivatives and mixtures thereof" .

Detergents are surfactants with cleaning properties in dilute solutions. Detergents are ions or molecules that contain both polar and nonpolar components. The polar end allows the detergent to dissolve in the water, whereas the nonpolar end solubilizes hydrophobic materials which are main target of the cleaning process.

Surfactant is the most important part of any cleaning composition. In general they are chemicals that, when dissolved in water or another solvent they orient themselves at the boundary between the liquid and a solid. Long nonpolar chain part of the surfactant molecule is attracted to oil, grease and dirt which are hydrophobic nature and another part of the molecule is attracted to water. The surfactant surround dirt until it is dislodged from the boundary. However surfactants are precipitated or removed from washing medium in presence of earth metal cations like Ca and Mg and loose their cleaning capabilities. Therefore earth alkaline metal cations must be removed from washing water to reveal full surfactant capability. Removal of earth alkaline metal cations are accomplished by complexation agents. The multivalent metal ions are surrounded from negative functionality ends of complexating agent. Thus, chelated metal ions remain tied up in solution where they will not use up the surfactants.

Common chelating agents used in cleaning compositions are phosphates, ethylene diamine tetra acetic acid (EDTA) its alkaline metal salts, citrate salts and zeolit. Among them phosphates are about to be banned due to environmental concerns. Zeolit and citrate are not strong enough complexating agent and are to be used in excess amounts. EDTA have been developed as phosphate substitue. However its high price and limitation due to health concern raise question of their replacement. Builders are often a good alternative to said complexation agents.

Builders are added to a cleaning composition to enhance efficiency of surfactants. They have a number of functions including softening, buffering, emulsifying and removal of multivalent cations from water. Builders provide a desirable level of alkalinity which aids in cleaning. They help emulsify oily or greasy soil by breaking them up to tiny globules and keep it from settling back on the cleaned surface.

One of the most used builder is sodium triphosphate, which is used on very large scale for this purpose. The heavy use of sodium triphosphate and its discharge into natural waters led to the problems of algae growth in excess of phosphorous, which cause oxygen depletion, consequently fish and plant death in stream and lakes. European Union introduced regulations to require biodegradability in all detergents and intend to ban phosphates in domestic products from 2013.

Existing alternatives to polyphosphates are of polyacrylate nature which are again suspect of being hazardous due to their synthetic nature and remaining monomer residues. There still exist a need to have builder with high binding capacity, less environmental concern and prefferably of organic origin to eliminate actuel and future concerns.

Humic acid is a principal component of humic substances, which are the major organic constituents of soil, peat and coal. It is produced by biodegradation of dead organic matter. It is not a single acid; rather, it is a complex mixture of many different acids containing carboxyl and phenolate groups, so that the mixture behaves dibasic or tribasic functionally .

A typical humic substance is a mixture of many molecules having aromatic, phenolic, carboxylic substituents linked together .

Below is a typical structure of unmodified humic acid having a variety of components including phenol, quinone, catechol and sugar moieties

Oxidized humic acid, which is the subject matter of the present invention, has differencies as some bonds are disrupted and some functionalities are oxidized. Oxidized humic acid has generally smaller molecular weight and increased number of hydroxy and carboxyl groups.

Oxidized humid acid compounds are used in the technic as fertilizer, regeneration of polluted grounds, animal breeding and water regeneration mainly. US5451244 R. Trowbridge teaches us use of humic acid in preparation of fertilizer compositions. Such humic acid containing compositions stimulates plant growth especially by humic acids water holding capacity.

US5201930 W. Campbell teaches us use of oxidized humic acid compositions in fertilizer. Such oxidized humic acid containing compositions serve as plant growth stimulant.

WO2010094985 to Lomoskiy et al teaches us preparation method of oxidized humic acid and its use for recultivation of heavy metal polluted land.

DE19624982 Pfueller et al teaches us use of humic acid and its oxidized forms for

purification of sewage water. Such treated water can be used as drinking water. There exist to date no usage of oxidized humic acid in cleaning compositions, especially in detergent compositions more particularly hard surface cleaning compositions.

It is therefore an object of the present invention, to provide alternative detergent builder for hard surface cleaning compositions that has no drawback of the marketed ones and superior to them.

DESCRIPTION OF DISCLOSURE

The present invention relates to a new use of oxidized humic acid.

By the search of an acceptable builder for use in cleaning compositions the present inventor surprisingly come to the finding that humic acid in oxidized form is an appropriate builder compound.

The present inventor has discovered that by adding oxidized humic acid compounds to the hard surface cleaning compositions foaming and cleaning capacity has increased.

To the best of our knowledge oxidized humic acid is not used in hard surface cleaning compositions. There exist no commercially available hard surface cleaning composition product containing oxidized humic acid on the market.

Due to the complex mixture character of humic acid and consequently complex mixture character of oxidized humic acid in the text the synonym "oxidized humic acid" will be standing for "oxidized humic acid , its salts, its derivatives and mixtures thereof". Further, the same synonym will be standing for compounds of oxidized humic acid and its salts and mixtures, which is derivatized afterwards; and derivatized humic acid which is oxidized afterwards and its salts and mixtures thereof.

In the present invention used oxidized humic acid may be in form of its salts. Due to the presence of carboxylic acids in the structure, salts may be cationic character of any type. The presence of carboxylate and phenolate groups give humic acid the ability to form complexes with ions such as Mg2+, Ca2+, Fe2+, Fe3+. This capability is enhanced by oxidation of humic acid.

In the past the complex binding capability of oxidized humic acid has not been measured. The present inventor additionally measured metal ion binding capacity and found that oxidized humic acid is an excellent builder with high earth alkaline metal cation capturing capability. By the search and measurements and further investigations the present inventor found that oxidized humic acids is by far superior to classic builder such as polyphosphate and even superior to the new generation builders which are of acrylic acid copolymer nature. Oxidized humic acid with 1350 mg Ca ion binding capacity per gram has stronger complexation capability than any other commercially available builder currently as shown herewith below.

Comparison of Ca2+ Complex Binding Capacities of Builders

Sodiumtripolyphosphate 198 mg Ca/g

Citric acid 270 mg Ca/g

Acrylic copolymer 400 mg Ca/g

Sulphonated acrylic copolymer 1150 mg Ca/g

Oxidized humic acid 1350 mg Ca/g Calcium ion binding capacity in mg with respect to per gram builder used in aqueous solutions is measured titrimetrically.

Classical builder compounds have their drawbacks such as polyphosphate, which is overfertilizing water sources. Polyacrylate are strong builders but due to their chemical origin some ecological reservations are existing. Considering its builder strength, relatively small amounts of oxidized humic acid is needed which is both economically and

environmentally advantageous. The ideal builder should have strong earth alkaline metal cation capturing capacity, should be of organic origin and ecologically acceptable. The present inventor unexpectedly found that humic acid in oxidized form is an excellent builder with high earth alkaline metal cation capturing capability. Furthermore oxidized humic acid has not ecologically nature originated drawbacks since it is of organic origin and decompose naturally in the natural environment.

Oxidized humic acid serve due to its complex organic structure as emulsifying agent, as a base for buffering purposes and furthermore as complexation agent. All these properties summed establish oxidized humic acid as a good builder.

The compositions disclosed in the present invention have improved foaming, thus cleaning properties due to high builder capabilities of oxidized humic acid used. Builders in detergent industry are compounds capable of capturing earth alkaline metal cations which are responsable for the hardness of water. Surfactants which are the main component of cleaners cannot reveal their full cleaning ca pabilities in presence of those cations. Oxidized humic acid is more prone to capture Mg2+ and Ca2+ cations then commercially already used builders. It is a good working, organic, with less ecological concern builder compound and superior to already existing builders.

Humic acid is originated from wood decomposition products. It is a renewable source and exist in large scale. Considering additionally its organic nature humic acid is an idea l compound as builder from economical and environmental perspective both. The presence of carboxylate and phenolate groups give humic acid the ability to form complexes with ions such as Mg2+, Ca2+, Fe2+, Fe3+.

This capability is enhanced by oxidation of humic acid. Therefore oxidized humic acid is superior to the humic acid as builder. The present inventor assume that additional oxidized phenol and carboxylate groups formed during oxidation procedure enhance the complexation capability . Measurements of the present inventor reveal that humic acid in oxidized form has higher earth alkaline metal cation complexation capability hence is a better builder . I n comparative cleaning tests achieved results support this fact as well. With oxidized humic acid replaced cleaning compositions are at least as good as classic builder containing hard surface cleaning compositions regarding cleaning capabilities. The present inventor assumes that oxidized humic acid has relatively more phenolate, carboxylate groups which are participating by complexation process.

Humic acid is a deep black colored substance due to high content of pigments, which makes it non desirable to use in cleaning compositions. This fact may be the reason for not using humic acid and staying away from its derivatives in field of cleaning compositions. Applying excess amount of oxidizing agent by synthesis of oxidized humic acid convert much of the pigments to noncolored substances. Oxidized humic acid obtained as such is light colored enough to be able to used for cleaning purposes. This color issue is an additional reason beside having higher complexation capacity for giving preference to oxidized humic acid and not to humic acid in the present invention.

Builders are compounds having the capability to capture the multivalent metal cations from water and remove them from the cleaning or washing medium. In the absence of these cations, surfactants, which are the main active washing agents, are not captured from these cations and can reveal their full washing strength. Builders have multiple anionic functional groups which are capable to bind by complexation earth alkaline metal cations. First commercially used builders were polyphosphates which are stil in use. They are able to capture multivalent metal cations and remove it from the medium by precipitating, since phosphate salts of these metal cations are less soluble in water. But due to environmental concerns related to overfertilizing water with phosphate and consuming of oxygen by water plants, which affect the life in water, polyphosphate builder are needed to be replaced with alternative builders. Existing alternatives are of polyacrylate nature which are again suspect of being hazardous due to their synthetic nature. Especially unreacted monomer residues remaining in polymers are main concern .

There still exist a need to have builder with high binding capacity, less environmental concern and prefferably of organic origin to eliminate actuel and future concerns.

According to the present invention there is provided hard surface cleaning compositions comprising oxidized humic acid, its salts and derivatives and their mixtures.

Oxidized humic acid used in hard surface cleaning compositions in the present invention are stable in nature. They maintain their builder properties in ambient conditions for a long time and at considerable harsh conditions for reasonable time period in comparison to the existing commercially available cleaning products. Oxidized humic acid containing hard surface cleaning compositions have same performance, durability, foaming capacity, cleaning capacity and stability compared to the equivalents in the marketed products. The oxidized humic acid containing compositions of the present invention are equal or superior to the commercially available hard surface cleaning composition products.

In present invention used oxidized humic acid amounts by weight are by far less than the existing commercially available composition products due to superior builder capacity. This makes its use more economical and with less environmental concern. Due to its stable nature oxidized humic acid can be used in liquid hard surface cleaning compositions of the present invention as well and last without degradation or negative effects for adequate time period.

According to present invention oxidized humic acid is used in compositions for cleaning glass, metal, plastic, ceramic, stone, tile, floor, sink, wash basin, toilet bowl, bathtube, bathroom, kitchen bench, building facade and similar surfaces. Oxidized humic acid of the present invention is used in hard surface cleaning compositions in liquid, solid and semisolid state as well. The application forms are including cream, gel, lotion, solution, colloid, suspension, powder, granul, tablet and capsul among others.

Oxidized humic acid of the present invention may be prepared from humic acid or humic acid containing mixtures like lignite, peat, coal and the like by addition of oxidizing agent. Particularly oxidized humic acid of the present invention is prepared starting from humic acid or humic acid source in a solvent in the presence of hydrogen peroxide.

Oxidized humic acid FTIR spectrums reveal in comparison to humic acid increased number of aliphatic hydrogen, phenolic groups and carbonyl moieties at respective wavelengths . This is indicating the cleavage and oxidation of bonds of humic acid and increase in carboxylic acid groups content.

In the present invention, oxidized humic acid is typically used in the form of aqueous solutions. As such it can be added to the liquid compositions directly from synthesis mixture without any treatment. As such oxidized humic acid containing reaction mixtures can be added directly to solid compositions for granulating purposes to achieve again solid compositions. Alternatively, said oxidized humic acid is used in solid form such as powder or granule. As such solid oxidized humic acid can be prepared from synthesis reaction mixture by removing solvent without any other separation of the reaction byproducts and reactants. Solid oxidized humic acid obtained that manner are used in solid hard surface cleaning

compositions by mixing, or in liquid hard surface cleaning compositions by dissolving in it.

Oxidized humic acid of the present invention can be used in hard surface cleaning compositions after separation from the synthesis reaction mixture.

Oxidized humic acid of the present invention added to the hard surface cleaning

compositions as reaction mixture in situ after the synthesis reaction are of the same or very similar performance with regard to complex binding capacity compared to separated oxidized humic acid.

Such compositions has no drawbacks with potential hydrogen peroxide residues . It is assumed that during the oxidation reaction all hydrogen peroxide is consumed and converted to percarboxylic acid residues of the oxidized humic acid compounds Remaining hydrogen peroxide is decomposed. As such this way of introduction of oxidized humic acid is convenient, feasable and economically advantageous. Both in application in liquid form hard surface cleaning compositions and solid form hard surface cleaning compositions.

Application of the synthesis reaction mixture to the liquid cleaning composition is very convenient due to being same physical state. Application to the solid cleaning composition is advantageously as being granulation solvent as well.

Application of solid nonseparated oxidized humic acid to the solid composition is of convenient being the same physical state as well. Solid form oxidized humic acid may be advantageous with respect of storage and handling. Separated form oxidized humic acid may be advantageous with respect of especially storage potential. Typically, hard surface cleaning compositions of the present invention are prepared by combining the ingredients with water to provide liquid solutions. Alternatively the components may be mixed in dry form.

The amounts of oxidized humic acid used in the hard surface cleaning compositions according to the present invention may be varied depending on the use purpose and desired concentrations. Oxidized humic acid used in the present invention compositions found to be effective starting from the concentration of 0.01 % of weight. Beyond 15 % of weight no additional effectiveness is to be observed as builder.

The amounts of oxidized humic acid used in the hard surface cleaning compositions according to the present invention may be within the range of 0.01% to 15% , prefferably %0.02 to % 10, most prefferably %0.05 to % 5 of weight.

Hard surface cleaning is the process of cleaning glass, metal, plastic, ceramic, stone, tile, flor, sink, wash basin, toilet bowl, bathtube, bathroom, kitchen bench, building facade and similar surfaces of any art. This is achieved either manually or using proper machine, tool or equipment. Hard surface cleaning reagents are usually in liquid or gel form and may be in powder, tablet form as well.

The hard surface cleaning compositions of the present invention comprise surfactants and builders as the main ingredients. Surfactants lower surface tension of water which has a wetting effect and help remove soil. Suitable surfactants for such use may be of anionic, cationic, nonionic and amphotheric nature .

Hard surface cleaning compositions are mainly comprised of surfactants, builders, and purposedly acids, base, bleaching agents, abrasives, perfume and dye among others.

Typical hard surface cleaners are glass cleaners, metal cleaners, building facade cleaners, toilet bowl cleaners, scouring agents and all purpose cleaners among others. Glass cleaners are expected to clean without rinsing. Typical window cleaning composition comprise alcohol, ethanol or propanol, surfactants to remove grease, ammonia, perfumes and dye.

Metal cleaners for ferrous metals the cleaning composition comprise chelating agent, abrasives, surfactant, acids, especially nonaggressive citric or phosphoric acid. Surfactants are usually modified fatty alcohols.

Building facade cleaners, for acid resistant facades for example brick acid type cleaners are used. These include phosphoric acid and hydrofluoric acid mixtures and surfactants. For acid sensitive facades like concrete strongly alkaline cleaners such as sodium hydroxide and thickeners are used.

Toilet bowl cleaners aim removal of calcium carbonate deposits by acids. Powdered cleaners contain solid acid salts such as sodium hydrogen sulfate. Liquid toilet bowl cleaners contain liquid acid such as hydrochloric, phosphoric or formic acids which dissolve calcium carbonate into its soluble salts.

Scouring agents comprise surfactants, water softeners and abrasive powders. Bleaching powders contain sodium hypochlorite releasing compounds.

All purpose cleaners are usually concentrated solution of surfactants and water softeners, which enhance the impact of surfactants in hard water. Typical surfactants used are alkylbenzenesulfonates, anionic detergents, modified fatty alcohols.

Surfactants are primary ingredients in a hard surface cleaning composition. Surfactant lowers surface tension of water, act as wetness agent which makes the soil removing possible. A combination of surfactants may be used as well . Hard surface cleaning composition of the present invention may comprise bleaching agents, hydrotropes, solvents, preservatives, antimicrobials, buffering agents, acids, base, bleaching agent, abrasives, salts, fragrances, perfume , softening agents, foaming agent, foam reducing agent and opacifying agent among others.

Hard surface cleaning compositions of the present invention may include additional additives known in the art such as surfactants whereas suitable surfactants for such use may be of anionic, cationic, nonionic and amphotheric nature. Additional ingredients may be added such as bleaching agents, hydrotropes, solvents, preservatives, antimicrobials, buffering agents, salts, opacifying agent, acids, base, abrasives, perfume and dye.

Builders combines with water hardness minerals and holds them in solution so that the minerals cannot combine with soils. Consequently minerals cannot combine with soils and leave insoluble spots or films on surfaces. Minerals themselves may leave spots on surfaces after washing, hence they are removed by builders as well. In the present invention used builder is oxidized humic acid which is the subject matter of the present invention. Oxidized humic acid may be used alone wherever possible and can be used in mixture of other builders. Being a strong builder oxidized humic acid may help reducing bulk builder amount.

Surfactant lowers surface tension of water, act as wetness agent which makes the soil removing possible. Suitable surfactants for such use may be of anionic, cationic, nonionic and amphotheric nature. Surfactants are used in the present invention in the range of %1 to %50 varying with respect of concentration or purpose of the compositions.

Anionic surfactants used in the hard surface cleaning compositions of the present invention comprise sulfate surfactants, linear alkyl benzene sulfonic acid , sodium lauryl ether sulfate, alpha olefin sulfonate, phosphate esters, sulfosuccinate surfactants, sodium dioctyl sulphosuccinate, sulfonate surfactants, alkyl benzene sulfonate, allylsulfate, sodium alkyl glyceryl ether sulfonate, alpha olefin sulfonate, linear alkyl benzene sulfonate, alcohol ether sulfate, dodecyl benzene sulfate, alkyl ethoxy sulfonate, alkylethoxyphosphate and mixtures thereof . Alkyl ethoxy sulfonate surfactants of the present invention used have average ethoxylation degree from 0.01 to 10, preferably from 0.02 to 4 and more preferably from 0.03 to 3.

Cationic surfactants used in the present invention help removing oily stain. Long chain quaternary ammonium compounds, cocoalkyl trimethyl ammonium methosulfate, lauryl amido propyl trimethyl ammonium methosulfate, polyglycolether, cocoammonium methosulfate, cetyl trimethyl ammonium chloride, betaines are the compounds of choice Nonionic surfactants used in the present invention are ethoxylated alcohols like linear alcohol ethoxylates,alkyl phenol ethoxylate octyl phenol ethoxylates, nonyl phenol ethoxylates, alkyl amine ethoxylate , alkyl polyglycoside like sodium gluconate, fatty alkanolamide, amine polyglycol ether, imidazolines , fatty amine oxide,.

Amphoteric surfactants used in the hard surface cleaning compositions of the present invention comprise alkyl dimethyl betaine, alkyl amidopropylbetaine and alkyl amine oxide. Sodium caprylamphopropionate , myristylamine oxide, Specifically Ν,Ν-dimethylacetic acid betaine, alkylamidepropyl-N,Ndimethyl-2-hydroxypropylsulfobetaine and alkylamidepropyl N, N-dimethylpropylsulfobetaine. Among them, lauramidepropyl-N,N-dimethylacetic acid betaine, myristamidepropyl-N, N-dimethylacetic acid betaine, alkylcarbobetaine,

alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamideamine-type betaine and alkylimidazoline-type betaine. Cocamidepropyl-N,N-dimethylacetic acid betaine and the like are particularly preferable in terms of detergency, foam producing ability and rinsing property.

Bleaching agents are active oxygen bleaches. They are removing stain to improve whitening by cleavage of bonds and oxidation. Sodium percarbonate, sodium perborate, sodium hypochlorite among others may be used in the present invention. For activating bleaching agents tetra acetyl ethylene diamine and similar compounds may be used. Bleaching agents are used in the present invention in the range of 1% to 30% by weight ,varying with respect of concentration or purpose of the commpositions. Abrasives used in the present invention compositions are zeolite , calcium carbonate, diatomaceous earth, kaolin and clay among others.

Hydrotropes are solubilizers maintaining the pouring characteristic by preventing separation of the composition into layers. Hydrotrope compounds of the present invention are xylene sulfonate, cumen sulfonate, glycol ether sulfate and the like. Hydrotropes are used in the present invention in the range of 1% to 20% by weight , varying with respect of

concentration or purpose of the commpositions.

Solvents are needed for preventing phasing out the composition and to dissolve some ingredients. Organic solvents are the main solvents used for this purpose and comprise for the present invention, ethanol, propanol, isopropanol, butoxy propoxy propanol, butoxy propanol, butoxy ethanol, , butyl diglycolether, benzyl alcohol, propoxy propoxy propanol, polypropylene glycol, ethers and diethers, alkoxylated glycols, C6-C16 glycol ethers, aliphatic branched alcohols, alkoxylated aliphatic alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols and mixtures thereof, diethylene glycol ethyl ether, propylene glycol methyl ether, diethylene glycol ethyl ether, mineral spirits and mixtures thereof. Used solvent amounts in the present invention may vary.

Acids may be used in the present invention compositions especially with regard to clean metal surfaces, especially lime stone. Preffered acids are among others, hydrochloride, sulfuric acid, phoshoric acid, hydrufluoric acid, acetic acid, oxalic acid, citric acid, formic acid. Additional alkalis may be used in handling greasy soils. In the present invention used alkali compounds are sodium carbonate, sodium hydroxide 2-amino-l-propanol, ammoniac, triethanolamine, aminomethyl propanol, morpholine among others.

Foam boosting compounds used in hard surface cleaning compositions of the present invention are amides like lauryl myristyl monoethanolamide, betaines like cocoamido propyl betaine, sulfobetaine and amine oxides such as alkyl- or alkenyl- amine oxides having a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, examplary , lauryl amido propyl amine oxide, myristal amido propyl amine oxide, lauryl dimethyl amine oxide, alkyl dimethyl amine oxides, cocodimethyl amine oxide, alkyl dihydroxyethyl amine oxide, coconut allyl dimethyl amine oxide, cocoamidopropyl amine oxide, cocoamide

diethanolamide, prefferably cocodinethyl amine oxide. These compounds add foam enhancement and stability, emulsification and viscosity building properties to the

compositions of the present invention. Foam boosting agents are used in the present invention in the range of 0.1% to 20% by weight .

Foam reducing agent inhibits formation of suds during the cleaning process. Siloxanes, paraffines, stearates, polydimethyl siloxanes, ethylene bis stearamide, silica, poly ethylene glycol, fatty alcohol, dimethicon, polyalkoxylated compounds of nonionic character are foam reducing agents of choice among others in the present invention compositions. Preservatives which can be optionally used in the present invention compositions at a concentration of 0 wt. % to 3 wt. % comprise benzalkonium chloride, benzethonium chloride, sodium benzoate, 5-bromo-5-nitro-l,3 dioxane, 2-bromo-2- nitropropane-1, 3-diol , alkyl trimethyl ammonium bromide; N- (hydroxymethyl)-N- (1, 3- dihydroxy methyl-2, 5-dioxo-4-imidaxolidinyl-N'- (hydroxy methyl) urea; 1-3-dimethyol- 5, 5-dimethyl hydantoin; formaldehyde; iodopropynl butyl carbamate, butyl paraben; ethyl paraben; methyl paraben; propyl paraben, mixture of methyl isothiazolinone/methyl-chloroisothiazoline; mixture of phenoxythanol/butyl paraben/methyl paraben/propylparaben ; 2-phenoxyethanol ; tris- hydroxyethyl-hexahydrotriazine ;

methylisothiazolinone ; 5-chloro-2-methyl-4-isothiazol- 3-one; 2-methyl-4-isothiazol- 3-one ; 1,2- dibromo-2, 4-dicyanobutane; 1- (3-chloroalkyl)-3, 5,7-triaza- azoniaadamantane and mixtures thereof. Further, compositions of the present invention may contain builder which act as a complexation agent as well, such as ethylene diamine tetra acetic acid (EDTA) and its salts. Preffered salts are alkali salts most preffered tetrasodium salt of EDTA. Polycarboxylated organic acids like citric acid and its salts may be used for complexation purposes as well beside polyphosphate and polyacrylate .

PH adjusting agents of basic nature such as sodium hydroxide, potassium hydroxide, alkali metal hydroxide, alkali metal carbonate, bicarbonate may be added to the present invention composition.

PH adjusting agents of of acidic nature, organic acids such as citric acid, fumaric acid, inorganic acids such as hydrochloric acid and sulfuric acid may be added to the present invention compositions.

Salts, Furthermore salts may be added to the compositions of the present invention. Said salts may be organic or inorganic nature such as sodium chloride, magnesium sulfate, calcium chloride, sodium citrate, sodium sulfate among others. Corrosion inhibitor helps protect machine parts and prevent corrosion of metals. I n the present invention used corrosion inhibitors are sodium silicate, zinc salts and bismuth salts.

Furthermore fragrances , perfume rheology modifier like carbopol, acrylic emulsion, xanthan gum and other components of convenient may be added.

Hard surface cleaning composition according to the present invention is prepared by mixing oxidized humic acid and surfactants and other desirable ingredients necessary mixed in water to obtain liquid hard surface cleaning composition of the present invention.

Alternatively a hard surface cleaning com position of the present invention is prepared by mixing oxidized humic acid and surfactants and other desirable ingredients necessary in solid state to obtain solid hard surface cleaning composition of the present invention. The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present invention. EXAMPLES

EXAMPLE A: Preparation of Oxidized Humic Acid

2 gramms of sodium salt of humic acid is dissolved in 45ml water. 5 ml of 30% aqueous solution of hydrogen peroxide is added and pH of the reaction solution is adjusted to 12 with sodium hydroxide. Reaction mixture is stirred at 70 C for 3 hours. After ceasing gas evolution reaction is considered to be completed. FTIR spectrum indicates increase of aliphatic hydrogen, phenolic groups and carbonyl moieties compared to humic acid FTIR spectrum.

Obtained rection mixture in solution is used directly in hard surface cleaning compositions. Alternatively reaction mixture solvent may be removed and remaining solid mixture may be used in hard surface cleaning compositions.

By a separate preparation, oxidized humic acid reaction mixture solution is removed by spray drying technic to obtain a powder, which is used in the compositions of the present inventions as solide reaction mixture. Another alternative is purification of oxidized humic acid from unreacted humic acid , reactant and reaction byproducts. This may be achieved by separation of unreacted reactants and reaction byproducts and removing solvent or precipitating oxidized humic acid before or after removal of reaction byproducts and unreacted reactants.

By a separate preparation , oxidized humic acid formed is separated from reaction mixture by removal of reaction solvent and subsequent ethanol addition as precipitation. Obtained powder which is called separated oxidized humic acid is used in the compositions of the present invention.

EXAMPLE 1: Preparation of Oxidized Humic Acid Containing Bath

Specific Liquid Hard Surface Cleaning Composition

Sodium lauryl ether sulfate 1%

Sodium octyl sulfate 1.5%

Benzisothiazolin preservative 0.08%

Oxidized humic acid 0.5% Hydrogen peroxide (%35 aqueous solution) 7%

Parfum 0.5%

Su 89.5%

Ingredients are mixed in water, from example A obtained oxidized humic acid reaction mixture solution is added directly after completion of oxidation reaction. Remaining water is added to obtain a solution and to complete %100 and pH is adjusted to 5.

This formul is specially prepared for surfaces specific to bathroom and similar environments.

Comparative Example 1 : Preparation of Polyacrylate Containing Bathroom Specific Liquid Hard Surface Composition Oxidized humic acid of Example 1 is replaced with 1% commonly used builder SOKALAN PA 30 CL which is a polyacrylate used as builder. Remaining ingredients are exactly the same with same ranges and same methode of preparation.

For the assessment of the effectiveness of oxidized humic acid containing compositions in comparison to oxidized humic acid substituted comparative compositions following test method is utilized:

Comparative Cleaning Tests

On a white colored hard surface, calcium oxalate , carbon black and water mixture is applied to have a black colorod surface and dried. 3 drops of each example 1 and comparative example 1 solution are dropped on respective spots and waited 3 minutes. Remaining solution is gently wiped off. There appears white color on the spots which strength depend on the cleaning strength of the respective hard surface cleaning compositions. The intensity of the white spots are evaluated by visual comparison.

Tests are performed according to above explained method on the example 1 and

comparative example 1 . The white spots appeared were of similar whiteness which led to the conclusion that oxidized humic acid containing hard surface cleaning compositions are at least as good as comparative hard surface cleaning compositions regarding cleaning capabilities. EXAMPLE 2: Preparation of Oxidized Humic Acid Containing Ferrous Metal Powder Light Duty Composition

Sodium carbonate 63%

Oxidized humic acid 3% Linear alcohol C12-13 1-3 ethoxylated 6%

*Metso pentabead 20 22%

Sodium gluconate 6%

*Metso pentabead 20 : mixture of sodium metasilicate and sodium hydroxide

Ingredients are mixed together. Oxidized humic acid powder, prepared by reaction solvent removal by spray drying technic is added to the composition.

Comparative Example 2 : Preparation of Sodium Tripolyphosphate Containing Ferrous Metal Powder Light Duty Composition

Oxidized humic acid of example 2 is replaced with %11 Sodium tripolyphosphate which is used as builder in cleaning compositions. Remaining ingredients are the same with same ranges (except Na2C03 is %55) and same methode of preparation.

Cleaning performance of example 2 is done by cleaning soiled ferrous metal surface.

Comparative cleaning tests performed with Example 2 and comparative example 2 revealing that oxidized humic acid containing composition is performing as good as the comparative composition 2 regarding cleaning capability.

EXAMPLE 3 : Preparation of Oxidized Humic Acid Containing Kitchen Specific Liquid Hard Surface Cleaning Composition

*Demelan AU 39 Bio 2% N,N -Dimethyldodecan 1-amine oxide 1%

*Arquad MCB 50 0.5% Caustic soda 0.5%

Oxidized humic acid 0.1%

Isopropyl alcohol 1%

Propylene glycol n-butyl ether 1% Water (to complete 100%) 93.9%

*Demelan AU 39 Bio: mixture of Quaternary ethoxylated fatty oil and ethoxylated fatty amine

*Arquad mcb 50: Mixture of Cocobenzyl dimethylammonium chloride and lauryl myristyl alcohol ethoxylate . Ingredients are mixed in water, from example A obtained separated oxidized humic acid which is prepared by removal of reaction solvent and in ethanol precipitated and added to the composition. Remaining water is added to obtain a solution and to complete 100%.

Comparative Example 3 : Preparation of EDTA Containing Liquid Kitchen Specific Hard Surface Cleaning Composition Oxidized humic acid of Example 3 is replaced with % 0.3 of commonly used complexation agent ethylene diamine tetra acetic acid tetrasodium salt Na4EDTA. Remaining ingredients are exactly the same with same ranges and same methode of preparation.

Comparative Tests

Cleaning performance of example 3 is done by cleaning burned grease . Thereby animal fat, butter and margarine are spread on tiles heated at 105C for 4 hours. Hard surface cleaning composition is applied onto soiled tiles, waited for 3 minutes and wiped using scrub tester and rinsed with water. For evaluation fotographs are used.

Comparative cleaning tests performed with Example 3 and comparative example 3 revealing that oxidized humic acid containing composition is performing as good as the comparative composition 3 regarding cleaning capability.

Claims

Claim 1. Use of oxidized humic acid, its salts and derivatives or mixtures thereof in hard surface cleaning compositions.

Claim 2. A hard surface cleaning composition according to claim 1, wherein hard surface cleaning composition is in liquid form.

Claim 3. A hard surface cleaning composition according to claim 1, wherein hard surface cleaning composition is in solid or semisolid form.

Claim 4. A hard surface cleaning composition according to claim 1, comprising from 0.01 % to 15% weight percent of oxidized humic acid , its salts and derivatives , prefferably from 0.02 % to 10 % weight percent of oxidized humic acid , its salts and derivatives, most prefferably from 0.05 to 5% weight percent of oxidized humic acid, its salts and derivatives.

Claim 5. A hard surface cleaning composition according to preceding claims, comprising addition of oxidized humic acid to the hard surface cleaning composition as reaction mixture after completion of oxidation of humic acid without any separation.

Claim 6. A hard surface cleaning composition according to claims 1 to 4, comprising addition of oxidized humic acid to the laundry composition as reaction mixture after completion of oxidation of humic acid and removal of reaction solvent.

Claim 7. A hard surface cleaning composition according to claims 1 to 4, comprising addition of separated oxidized humic acid to the hard surface cleaning composition.

Claim 8. A hard surface cleaning composition according to preceding claims, which further comprises a surfactant or surfactants.

Claim 9. A hard surface cleaning omposition according to preceding claims, which further comprises bleaching agents, hydrotropes, solvents, preservatives, antimicrobials, buffering agents, salts, fragrances, perfume , foaming agent, foam reducing agent , base, acid and opacifying agent.

Claim 10. A liquid hard surface cleaning composition according to claim 1, claim2 and claims 4 to 9, comprising a) from 1% to 35 % by weight of surfactant or surfactants

b) from 0.01% to 15% by weight of oxidized humic acid, its salts and derivatives c)water

Claim 11. A liquid hard surface cleaning composition according to claim 10, comprising a) from 2% to 30 % by weight of surfactant or surfactants

b) from 0.02% to 10 % by weight of oxidized humic acid, its salts and derivatives c)water

Claim 12. A liquid hard surface cleaning composition according to claim 1, claim2 and claims 4 to 9, comprising a) from 3% to 25% by weight of anionic surfactant

b) from 1% to 15% by weight of bleaching agent

c) from 0.02% to 10% by weight of oxidized humic acid, its salts and derivatives d) water

Claim 13. A liquid hard surface cleaning composition according to claim 12, comprising a) from 1% to 25% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of sodium octyl sulfate

c) from l% to 10% by weight of aqueous hydrogen peroxide solution

d) from 0.01% to 5 % by weight of preservative which is selected from isothiazoline compounds

e) from 0.02% to 10% by weight of oxidized humic acid, its salts and derivatives f) water to

Claim 14. A liquid hard surface cleaning composition according to claim 10, comprising a) from 1% to 35 % by weight of surfactant or surfactants

b) from 0.01% to 15% by weight of oxidized humic acid, its salts and derivatives c) water wherein , oxidized humic acid is added to the hard surface cleaning composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.

Claim 15. A liquid hard surface cleaning composition according to claim 12, comprising a) from 3% to 25% by weight of anionic surfactant

b) from 1% to 15% by weight of bleaching agent

c) from 0.02% to 10% by weight of oxidized humic acid, its salts and derivatives d) water wherein, oxidized humic acid is added to the hard surface cleaning composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.