Use of oxidized humic acid its salts and derivatives in laundry compositions

Abstract

 The present invention relates to the field of laundry compositions. In particular this invention relates to the use of oxidized humic acid compounds, its salts and derivatives or its mixtures, in laundry compositions. Such cleaning compositions have improved foaming capacities due to excellent builder properties of oxidized humic acid, its salts and derivatives. 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 of fabric, cloth, carpet, fibre, woven or nonwoven textile of any art.

Description

FIELD OF THE INVENTION

[0001] This application relates to laundry compositions.

[0002] Particularly this application relates to the use of oxidized humic acid, its salts its derivatives and mixtures thereof in laundry compositions.

[0003] This application relates to the laundry compositions ,whereas oxidized humic ,its salts its derivatives and mixtures thereof is added to the laundry composition in situ after synthesis or after separation of oxidized humic acid from reaction mixture.

[0004] This application relates to the synthesis of oxidized humic acid which is compatible for the use in laundry compositions.

BACKGROUND OF THE INVENTION

[0005] Hereinafter in the text the synonym "oxidized humic acid" will be standing for "oxidized humic acid , its salts, its derivatives and mixtures thereof".

[0006] 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.

[0007] 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. Surfactant surround dirt until it is dislodged from the boundary.

[0008] 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.

[0009] 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.

[0010] 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 used in excess amounts. EDTA have been developed as phosphate substitue. However its high price and limitation due to health concerns raise question of their replacement. Builders are often a good alternatives to said complexation agents.

[0011] Builders are added to a cleaning composition to enhance efficiency of surfactants. They have a number of functions including softening, buffering, emulsifying and removing multivalent cations from water. Builders provide a desirable level of alkalinity which aids in cleaning. Builders help emulsify oily or greasy soil by breaking them up to tiny globules and keep them from settling back on the cleaned surface.

[0012] 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 problem 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.

[0013] Existing alternatives to polyphosphates are of polyacrylate nature which are again suspect of being hazardous due to their synthetic nature and remaining monomer residues.

[0014] 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.

[0015] 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.

[0016] A typical humic substance is a mixture of many molecules having aromatic, phenolic, carboxylic substituents linked together.

[0017] Below is a typical structure of unmodified humic acid having a variety of components including phenol, quinone, catechol and sugar moieties:

[0018] 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.

[0019] Oxidized humid acid compounds are used in the technic as fertilizer, regeneration of polluted grounds, animal breeding and water regeneration mainly.

[0020] 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

[0021] 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 Lomoskiy et al teaches us preparation method of oxidized humic acid and its use for recultivation of heavy metal polluted land.

[0022] 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.

[0023] There exist to date no usage of oxidized humic acid in cleaning compositions especially in detergent compositions more particularly laundry compositions.

[0024] It is therefore an object of the present invention to provide alternative detergent builder for laundry compositions that has no drawback of the marketed ones and superior to them.

DESCRIPTION OF DISCLOSURE

[0025] The present invention relates to a new use of oxidized humic acid.

[0026] 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.

[0027] The present inventor has discovered that by adding oxidized humic acid compounds to the laundry compositions foaming and cleaning capacity has increased.

[0028] To the best of our knowledge oxidized humic acid is not used in laundry compositions. There exist no commercially available laundry composition product containing oxidized humic acid on the market.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] In the past no complex binding capability of oxidized humic acid is 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 1350mg 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:

[0033] 

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

[0034] Calcium ion binding capacity in mg with respect to per gram builder used in aqueous solutions is measured titrimetrically.

[0035] Classical builder compounds have their drawbacks such as polyphosphate, which are overfertilizing water sources. Polyacrylates are strong builders but due to their chemical origin some ecological reservations are stil existing. Considering its builder strength, relatively small amounts of oxidized humic acid is needed which is both economically and environmentally advantageous.

[0036] 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 such ecologically nature originated drawbacks since it is of organic origin and decompose naturally in the natural environment.

[0037] 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.

[0038] 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 capabilities in presence of those cations. Oxidized humic acid is more prone to capture Mg2+ and Ca2+ cations than commercially already used builders. It is a good working, organic, with less ecological concern builder compound thus superior to already existing builders.

[0039] Humic acid is originated from wood decomposition products. It is a renewable source and existing in large scale. Considering additionally its organic nature humic acid is an ideal compound as builder from economical and environmental aspect both.

[0040] The presence of carboxylate and phenolate groups give humic acid the ability to form complexes with ions such as Mg2+, Ca2+, Fe2+, Fe3+.

[0041] 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. In comparative washing tests achieved results support this fact as well. With oxidized humic acid replaced cleaning compositions are at least as good as classic builder containing laundry compositions regarding cleaning capabilities. We assume that oxidized humic acid has relatively more phenolate, carboxylate groups which are participating by complexation process.

[0042] 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.

[0043] 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 complete washing strength.

[0044] 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 were 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 .

[0045] 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.

[0046] According to the present invention there is provided a laundry composition comprising oxidized humic acid, its salts and derivatives and their mixtures.

[0047] Oxidized humic acid used in laundry 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 laundry 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 laundry composition products.

[0048] 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 laundry compositions of the present invention as well and last without degradation or negative effects for adequate time period.

[0049] According to the present invention oxidized humic acid is used in compositions for cleaning fabrics, clothes, carpets, woven or nonwoven type of textile any art.

[0050] Oxidized humic acid of the present invention is used in laundry compositions in liquid, solid and semisolid state as well. The application forms are including cream, gel, lotion, solution, colloid ,suspension, powder, granul, tablet, pouch and capsul among others. Pouch and tablet forms may include multicompartments comprising liquid, solid or gel forms. 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.

[0051] 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.

[0052] 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.

[0053] 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 obtain solid compositions.

[0054] 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 laundry compositions or in liquid laundry compositions by dissolving in it.

[0055] Oxidized humic acid of the present invention can be used in laundry compositions after separation from the synthesis reaction mixture.

[0056] Oxidized humic acid of the present invention added to the laundry 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.

[0057] 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 laundry compositions and solid form laundry compositions. Application to the liquid composition is very convenient due to being same physical state. Application to the solid composition is advantageously as being granulation solvent as well.

[0058] Application of solid nonseparated oxidized humic acid to the solid composition is of convenient being the same physical state. Solid form oxidized humic acid is advantageous with respect of storage and handling. Separated form oxidized humic acid may be advantageous with respect of especially storage potential.

[0059] Typically, laundry 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.

[0060] The amounts of oxidized humic acid used in the laundry compositions according to the present invention may be varied depending on the use purpose and desired concentrations.

[0061] 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.

[0062] The amounts of oxidized humic acid used in the laundry 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.

[0063] Laundry is the process of cleaning fabric, cloth, carpet, fibre, woven or nonwoven textile of any art. This is achieved either by hand or using washing machine.

[0064] Hand laundry detergents are usually liquid or in gel form. Washing machine detergents may be in powder, tablet, gel, liquid form. Hand laundry liquids are usually highly foaming mixture of surfactants with low skin irritation.

[0065] Washing machine used detergents contain mainly non bubbling surfactants which may be nonionic character or low foaming type of other surfactants and water hardness remover. Too much suds will be causing the washing machine to overflow and smother the water action necessary for cleaning.

[0066] Surfactants lower surface tension of water which has a wetting effect and helps remove soil.

[0067] The laundry compositions of the present invention comprise surfactants and builders as the main ingredient. Suitable surfactants for such use may be of anionic, cationic, nonionic and amphotheric nature.

[0068] Hand laundry compositions are mainly comprised of surfactants, stability agents, preservatives, foaming agents, foam boosting agents, skin compatibility agents..

[0069] Stability and dispensing aids are added to keep the product homogeneous under varying storage conditions. Hydrotropes and salts are often used.

[0070] Preservatives are added if needed in small amounts to help prevent any microbiological growth in the product.

[0071] Hand laundry composition of the present invention comprise as ingredients beside the present invention builder oxidized humic acid, surfactants , hydrotropes, solvents, preservatives, antimicrobials, buffering agents, salts, fragrances, perfume, foam booster, enzymes, dye transfer inhibitor, redeposition inhibitor and skin compatibility agents.

[0072] Surfactants are primary ingredients in a liquid hand laundry detergent. Often a combination of surfactants is used.

[0073] Washing machine laundry composition of the present invention comprise as ingredients beside the present invention builder oxidized humic acid , surfactants, corrosion inhibitor, additional alkali, perfume, bleaching agents, hydrotropes, solvents, preservatives, buffering agents, salts, softening agents, foam reducing agents, opacifying agents, dye transfer inhibitor, redeposition inhibitor, enzymes, and processing aids.

[0074] Surfactant lowers surface tension of water, act as wetness agent which makes the soil removing possible. Nonionic surfactant are used in washing machine compositions because they have lowest sudsing effect.

[0075] The laundry compositions of the present invention beside the present invention builder oxidized humic acid 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 are among others bleaching agents, hydrotropes, solvents, preservatives, antimicrobials, buffering agents, salts, fragrances, perfume, softening agents, foaming agent, foam reducing agent, opacifying agent, dye transfer inhibitor, redeposition inhibitor and enzymes.

[0076] 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 commpositions.

[0077] Anionic surfactants used in the laundry compositions of the present invention comprise sulfate surfactants, linear alkylbenzene 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, sodium lauryl ether sulfate, 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.

[0078] Cationic surfactants are generally used as fabric softeners. But small amounts of addition helps removing oily stain in the present invention compositions. 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.

[0079] 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,.

[0080] Amphoteric surfactants used in the laundry compositions of the present invention comprise alkyl dimethyl betaine, alkyl amidopropylbetaine and alkyl amine oxide. Specifically N,N-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.

[0081] 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 are bleaching agents which 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 40% by weight ,varying with respect of concentration or purpose of the commpositions.

[0082] 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.

[0083] 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 diglycoether, 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. Used solvent amounts in the present invention may vary.

[0084] Alkali may be used additionally in handling greasy soils. In the present invention used alkali compounds are sodium carbonate, caustic soda among others.

[0085] Softening agents impart softness, reduced static electric and reduced crinkling. Softening agents used in the present invention compositions comprise long chain amine, long chain quaternary ammonium compounds, diethyls ester dimethyl ammonium chloride and poly dimethyl siloxane among others.

[0086] Foam boosting compounds used in hand wash laundry 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 ,exemplary, 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 and cocoamide diethanolamide , prefferably cocodimethyl 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.

[0087] Foam reducing agent inhibits formation of suds during the washing cycle. Siloxanes, paraffines, stearates, polydimethyl siloxanes, ethylene bis stearamide, silica, poly ethylene glycol , fatty alcohol, polyakoxylated compounds of nonionic character are foam reducing agents of choice among others in the present invention compositions.

[0088] Dye transfer inhibitors are used to keep the textiles their original color by binding to free dye molecules and preventing them to redeposited onto other parts of textiles. Polyvinyl pyrrolidone and polyvinyl pyrrolidone N-oxide are the dy transfer inhibitor of choice among others,of the present invention compositions.

[0089] Redeposition inhibitor prevents soil from being redeposited onto textiles during wash cycle. Carboxy methyl cellulose, polyvinyl pyrrolidone, poly ethylene glycol, polyvinyl alcohol are redeposition inhibitor of choice among others ,of the present invention compositions.

[0090] Enzymes may be added especially to solid laundry compositions of the present invention composition comprising amylase, lipase and protease among others.

[0091] Preservatives which can be optionally used in the present invention are compositions at a concentration of 0 wt. % to 3 wt. The preservatives used in the present invention may comprise benzalkonium chloride; benzethonium chloride; sodium benzoate; 5-bromo-5-nitro-1,3 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 chloride ; sodium benzoate and mixtures thereof.

[0092] Antimicrobials may be used to prevent disease and odour especially of hand washing laundry compositions. Quaterammonium chloride, alcohol among others may be used for this purpose in the present invention compositions.

[0093] Buffering 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.

[0094] Buffering agent of acidic nature such as citric acid, fumaric acid, organic acids and inorganic acids such as hydrochloric acid and sulfuric acid may be added to the present invention composition.

[0095] Salts added to the compositions of the present invention may be organic or inorganic nature such as sodium chloride, magnesium sulfate, calcium chloride, sodium citrate, sodium sulfate among others.

[0096] Corrosion inhibitor helps protect machine parts and prevent corrosion of metals. In the present invention used corrosion inhibitors are sodium silicate and other suitable compounds of respective equipment.

[0097] Optical brighteners enhance the light reflected from fabric surface by emitting blue light. Coumarin, stilben, aminotriazine compounds are optical brighteners of the choice among others in the present invention compositions.

[0098] Surfactants interact with skin by binding to skin protein and cause swelling. An example is sodium lauryl sulfate which is limiting its use by hand wash detergents. A solution to this problem constitute use of mild surfactants, use of ethoxylated alcohols and skin compatibility agents.

[0099] Skin compatibility agents of the present invention may comprise methyl ester sulfonate, coco fatty acid methyl ester sulfonate, betaine compounds prefferably cocamidepropyl-N,N-dimethylacetic acid.

[0100] Furthermore fragrances, perfume and other components of convenient may be added.

[0101] A Laundry 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 laundry composition of the present invention.

[0102] Alternatively a laundry composition of the present invention is prepared by mixing oxidized humic acid and surfactants and other desirable ingredients necessary in solid state to obtain solid laundry composition of the present invention.

[0103] 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

[0104] 2 gramms 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.

[0105] Obtained rection mixture in solution is used directly in laundry compositions. Alternatively reaction mixture solvent may be removed and remaining solid mixture may be used in laundry compositions.

[0106] 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.

[0107] 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.

[0108] 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 Light Duty Liquid Laundry Composition

[0109] 

Linear alkyl benzene sulfonic acid Sodium salt	7.3 %
Caustic soda	2.3 %
Sodium lauryl ether sulphate	3.5 %
(with 2 moles of ethyleneoxide)
Coconut fatty acid	1.5 %
*Palmera B1212	3.5 %
*Polyquart SD 09	3.5 %
*Opacifier B1 E	3.0 %
*Nipacide 15 TR	0.08 %
Oxidized humic acid	0.1 % (as reaction mixture solution)
Water	75.3%

*Polyquart SD 09 : Diallyldimethyl ammonium chloride-propenamide copolymer *Palmera B1212 : Oleochemical alcohol (medium degree ethoxylated) *Opacifier B1 E: Antifoam emulsion comprising water, polydimethylsiloxane, treated amorphous silica, polyethylene glycol stearyl ether, polyethylene glycol stearate. *Nipacide 15 TR: antibacterial mixture of 5-Chloro-2-Methyl-2H-isothiazol-3-one and 2-Methyl-2H-isothiazol-3-one

[0110] 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 8.

[0111] Comparative Example 1: Preparation of EDTA Containing Liquid Laundry Composition

[0112] Oxidized humic acid of Example 1 is replaced with % 0.1 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 Washing Tests

[0113] For the assessment of the effectiveness of oxidized humic acid containing compositions in comparison to oxidized humic acid substituted comparative compositions, washing tests with selected stains are carried out in the same conditions.

Tests are conducted via Scheffe Panel Score Test.

[0114] Accordingly, cotton fabrics stained with selected stains are cut equally. 3kg of stained cotton fabric is put in washing water having water hardness corresponding to 150ppm Ca2+ cation. 100g of oxidized humic acid containing composition solution of Example 1 is added and washed in automatic washing mashine at 40C and dried.

[0115] Same procedure is applied to 100g of Na4EDTA containing Comparative Example 1 composition solution.

[0116] Thereafter stain removing capacities of both washings are compared by eye sighting according to Scheffe Panel Score Units on the following scale:

0

No difference

1

I think this is better

2

I know this is a little better

3

I know this is much better

4

I know this is very much better

Comparative Washing Results of Example 1 and Comparative Example 1 Compositions of Selected Stains

Stains Comparative Scheffe values of Example 1/Comparative example 1

[0117] 

Soiled motor oil	3.25
Lipstick	2.5
Sour cherry	1.0
chocolate	1.88
Grass	1.63
Ketchup	2.0
Mud	2.63

[0118] As can be seen from comparative washing test results oxidized humic acid containing laundry compositions are at least as good as comparative laundry compositions, regarding cleaning capabilities, even better.

EXAMPLE 2: Preparation of Oxidized Humic acid Containing Powder Laundry Composition

[0119] 

Linear alkyl benzene sulfonic acid sodium salt	7.7%
Caustic soda(49% aqueous solution	2%
Sodium silicate	4%
Ethoxylated linear oleochemical alcohol	1.5%
Oxidized humic acid	0.5%
Sodium carbonate	17.5%
Sodium percarbonate	17%
Tetra acetyl ethylene diamine	1.6%
Defoamer silicon	1%
Enzyme mixture	11%
Perfume	0.3%
Sodium sulfate	45.1%

[0120] 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 Polyacrylic Acid Sodium Builder Containing Powder Laundry Composition

[0121] Humic acid of example 2 is replaced with %1.5 SOKALAN PA 30CL which is a low molecular weight polyacrylic acid sodium polymer used as builder in cleaning compositions. Remaining ingredients are exactly the same with same ranges and same methode of preparation.

[0122] Comparative washing tests same as in Example 1 are performed with Example 2 and comparative example 2 revealing that oxidized humic acid containing composition is performing at least as good as comparative laundry composition, regarding cleaning capability.

EXAMPLE 3: Preparation of Oxidized Humic Acid Containing Heavy Duty Liquid Laundry Composition

[0123] 

Hydrogenated coconut fatty acid	2.5%
Linear alkyl benzene sulfonic acid sodium salt	8.8%
Caustic soda(49% aqueous solution)	2.8%
Sodium lauryl ether sulfate (2 moles of ethoxy)	3.6%
Ethoxylated linear oleochemical alcohol	9%
Oxidized humic acid	0.5%
Borax decahydrate	1%
Propylene glycol	1.5%
Cumene sulfonate	0.5%
Defoamer silicon	0.2%
Enzyme mixture	1.7%
Perfume	1%
Water (to complete to %100)	66.9%

[0124] Ingredients are mixed in water, from example A obtained oxidized humic acid is separated from reaction mixture 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 Polyacrylic Acid Sodium Builder Containing Liquid Laundry Composition

[0125] Humic acid of example 2 is replaced with 5% ACUSOL 460NK which is a polyacrylic acid sodium copolymer used as builder in cleaning compositions. Remaining ingredients are exactly the same with same ranges and same methode of preparation.

[0126] Comparative washing tests same as in Example 1 are performed with Example 3 and comparative example 3 revealing that oxidized humic acid containing composition is performing at least as good as comparative laundry compositions, regarding cleaning capabilities.

Claims

1. Use of oxidized humic acid, its salts and derivatives or mixtures thereof in laundry compositions.

2. A laundry composition according to claim 1, wherein laundry composition is in liquid form.

3. A laundry composition according to claim 1, wherein laundry composition is in solid or semisolid form.

4. A laundry 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.

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

6. A laundry 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.

7. A laundry composition according to claims 1 to 4, comprising addition of separated oxidized humic acid to the laundry composition.

8. A laundry composition according to preceding claims, which further comprises a surfactant or surfactants.

9. A laundry composition according to preceding claims, which further comprises bleaching agents, hydrotropes, solvents, preservatives, antimicrobials, buffering agents, salts, fragrances, perfume, softening agents, foaming agent, foam reducing agent, opacifying agent, dye transfer inhibitor, redeposition inhibitor and enzymes.

10. A liquid laundry composition according to claim 1, claim 2 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

11. A liquid laundry 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

12. A liquid laundry composition according to claim 1, claim2 and claims 4 to 9,
comprising

a) from 2% to 30% by weight of anionic surfactant

b)from 1% to 10% by weight of oleochemical alcohol

c) from 1% to 15 % by weight of cationic surfactant

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

e) water

13. A liquid laundry composition according to claim 12, comprising

a) from 5% to 25% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 10% by weight of medium degree ethoxylated oleochemical alcohol

d) from 1% to 10 % by weight of diallyldimethyl ammonium chloride-propenamide copolymer

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

f) water

14. A liquid laundry 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 laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.

15. A liquid laundry composition according to claim 12, comprising

a) from 2% to 30% by weight of anionic surfactant

b)from 1% to 10% by weight of oleochemical alcohol

c) from 1% to 15 % by weight of cationic surfactant

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

e) water

wherein , oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.

16. A liquid laundry composition according to claim 13, comprising

a) from 5% to 25% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 10% by weight of medium degree ethoxylated oleochemical alcohol

d) from 1% to 10 % by weight of diallyldimethyl ammonium chloride-propenamide copolymer

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

f) water

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.

17. A liquid laundry 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 laundry composition as reaction mixture after completion of oxidation of humic acid and removal of reaction solvent.

18. A liquid laundry composition according to claim 12, comprising

a) from 2% to 30% by weight of anionic surfactant

b)from 1% to 10% by weight of oleochemical alcohol

c) from 1% to 15 % by weight of cationic surfactant

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

e) water

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid and removal of reaction solvent.

19. A liquid laundry composition according to claim 13, comprising

a) from 5% to 25% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 10% by weight of medium degree ethoxylated oleochemical alcohol

d) from 1% to 10 % by weight of diallyldimethyl ammonium chloride-propenamide copolymer

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

f) water to

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid and removal of reaction solvent.

20. A liquid laundry 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, separated oxidized humic acid is added to the laundry composition.

21. A liquid laundry composition according to claim 12, comprising

a) from 2% to 30% by weight of anionic surfactant

b)from 1% to 10% by weight of oleochemical alcohol

c) from 1% to 15 % by weight of cationic surfactant

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

e) water

wherein, separated oxidized humic acid is added to the laundry composition.

22. A liquid laundry composition according to claim 13, comprising

a) from 5% to 25% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 10% by weight of medium degree ethoxylated oleochemical alcohol

d) from 1% to 10 % by weight of diallyldimethyl ammonium chloride-propenamide copolymer

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

f) water
wherein, separated oxidized humic acid is added to the laundry composition.

23. A liquid laundry composition according to claim 1, claim 2 and claim 4 to 9, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1% to 5% by weight of enzyme

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

e) from 0.1% to 5% by weight of hydrotrope compound

f) water

24. A liquid laundry composition according to claim 23, comprising

a) from 3% to 15% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 20% by weight of ethoxylated oleochemical alcohol

d) from 0.1% to 5% by weight of enzyme

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

f) from 0.1% to 5% by weight of cumene sulfonate

g) water

25. A liquid laundry composition according to claim 23, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1% to 5% by weight of enzyme

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

e) from 0.1% to 5% by weight of hydrotrope compound

f) water

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.

26. A liquid laundry composition according to claim 24, comprising

a) from 3% to 15% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 20% by weight of ethoxylated oleochemical alcohol

d) from 0.1% to 5% by weight of enzyme

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

f) from 0.1 % to 5% by weight of cumene sulfonate

g) water

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.

27. A liquid laundry composition according to claim 23, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1% to 5% by weight of enzyme

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

e) from 0.1% to 5% by weight of hydrotrope compound

f) water

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid and removal of reaction solvent.

28. A liquid laundry composition according to claim 24, comprising

a) from 3% to 15% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 20% by weight of ethoxylated oleochemical alcohol

d) from 0.1% to 5% by weight of enzyme

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

f) from 0.1 % to 5% by weight of cumene sulfonate

g) water

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid and removal of reaction solvent.

29. A liquid laundry composition according to claim 23, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1% to 5% by weight of enzyme

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

e) from 0.1% to 5% by weight of hydrotrope compound

f) water

wherein, separated oxidized humic acid is added to the laundry composition.

30. A liquid laundry composition according to claim 24, comprising

a) from 3% to 15% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 20% by weight of ethoxylated oleochemical alcohol

d) from 0.1% to 5% by weight of enzyme

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

f) from 0.1 % to 5% by weight of cumene sulfonate

g) water

wherein, separated oxidized humic acid is added to the laundry composition.

31. A solid laundry composition according to claim 1 and claims 3 to 9, whereas said solid composition may be in powder, granul, capsulated, tabletted form

32. A solid laundry composition according to claim 1 and claims 3 to 9, comprises

a) from 1% to 30 % by weight of surfactant or surfactants

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

33. A solid laundry composition according to claim 1 and claims 3 to 9, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1 to 5% by weight of enzyme

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

e) from 3% to 40% by weight of sodium carbonate

f) from 0.5 % to 5% by weight of defoamer compound

g)from 3% to 30% by weight of bleaching agent

h)from 1% to 15% by weight of silicate

34. A solid laundry composition according to claim 33, comprising

a) from 3% to 25% by weight of linear alkyl benzene sulfonic acid sodium salt

b)from 1% to 20% by weight of ethoxylated oleochemical alcohol

c) from 0.1 to 5% by weight of enzyme mixture

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

e) from 3% to 40% by weight of sodium carbonate

f) from 0.5 % to 5% by weight of silicon based defoamer compound

g)from 3% to 30% by weight of sodium percarbonate

h)from 1% to 15% by weight of sodium silicate

i)from 0.2 % to 5% by weight of bleaching agent activating agent

35. A solid laundry composition according to claim 33, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1 to 5% by weight of enzyme

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

e) from 3% to 40% by weight of sodium carbonate

f) from 0.5 % to 5% by weight of defoamer compound

g)from 3% to 30% by weight of bleaching agent

h)from 1% to 15% by weight of silicate

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.

36. A solid laundry composition according to claim 34, comprising

a) from 3% to 25% by weight of linear alkyl benzene sulfonic acid sodium salt

b)from 1% to 20% by weight of ethoxylated oleochemical alcohol

c) from 0.1%to 5% by weight of enzyme mixture

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

e) from 3% to 40% by weight of sodium carbonate

f) from 0.5 % to 5% by weight of silicon based defoamer compound

g)from 3% to 30% by weight of sodium percarbonate

h)from 1% to 15% by weight of sodium silicate

i)from 0.2% to 5% by weight of bleaching agent activating agent

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.

37. A solid laundry composition according to claim 33, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1 to 5% by weight of enzyme

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

e) from 3% to 40% by weight of sodium carbonate

f) from 0.5 % to 5% by weight of defoamer compound

g)from 3% to 30% by weight of bleaching agent

h)from 1% to 15% by weight of silicate

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid and removal of reaction solvent.

38. A solid laundry composition according to claim 34, comprising

a) from 3% to 25% by weight of linear alkyl benzene sulfonic acid sodium salt

b)from 1% to 20% by weight of ethoxylated oleochemical alcohol

c) from 0.1 to 5% by weight of enzyme mixture

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

e) from 3% to 40% by weight of sodium carbonate

f) from 0.5 % to 5% by weight of silicon based defoamer compound

g)from 3% to 30% by weight of sodium percarbonate

h)from 1% to 15% by weight of sodium silicate

i)from 0.2 to 5% by weight of bleaching agent activating agent

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid and removal of reaction solvent.

39. A solid laundry composition according to claim 33, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1 to 5% by weight of enzyme

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

e) from 3% to 40% by weight of sodium carbonate

f) from 0.5 % to 5% by weight of defoamer compound

g)from 3% to 30% by weight of bleaching agent

h)from 1% to 15% by weight of silicate

wherein, separated oxidized humic acid is added to the laundry composition.

40. A solid laundry composition according to claim 34, comprising

a) from 3% to 25% by weight of linear alkyl benzene sulfonic acid sodium salt

b)from 1% to 20% by weight of ethoxylated oleochemical alcohol

c) from 0.1 to 5% by weight of enzyme mixture

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

e) from 3% to 40% by weight of sodium carbonate

f) from 0.5 % to 5% by weight of silicon based defoamer compound

g)from 3% to 30% by weight of sodium percarbonate

h)from 1% to 15% by weight of sodium silicate

i)from 0.2 to 5% by weight of bleaching agent activating agent

wherein, separated oxidized humic acid is added to the laundry composition.

41. A tabletted laundry composition according to preceding claims.

42. A multicompartmental tabletted laundry composition according to preceding claims, wherein tabletted form is comprising at least two solid, liquid or gel form compartments.

43. A laundry composition according to preceding claims, wherein said composition is in pouch form.

44. A multicompartmental pouch laundry composition according to preceding claims, wherein pouch form is comprising at least two solid, liquid or gel form compartments.

45. A cleaning composition as claimed in any preceding claims, having application preferably on fabrics, clothes, carpets, woven or nonwoven type of textile.

Amended claims

Amended claims in accordance with Rule 137(2) EPC.

1. Use of oxidized humic acid, or its salts as a builder in laundry compositions.
The term "Derivatives" was removed to avoid humic acid involvement from whole of the claim set. In agreement with the examiner, the term "as builder" was added in order to underline the functionality of oxidized humic acids as builder.

2. A laundry composition according to claim 1, wherein laundry composition is in liquid, solid or semisolid form.
Claim 2 and 3 of previous claim set was united. This claim indicates the forms that oxidized humic acid comprising laundry compositions can take, as stated in description part page 8.

3. A laundry composition according to claim 1, comprising, from 0.02 % to 10 % weight percent of oxidized humic acid or its salts, prefferably from 0.05 % to 5 % weight percent of oxidized humic acid or its salts.
The section "0.01% to 15%"weight percent of oxidized humic acid" in previous claim 4 was removed to specify that oxidized humic acid can be used as efficient builder in amounts 10% or less by weight of the total composition.

4. A laundry composition according to preceding claims, comprising addition of oxidized humic acid or its salts to laundry composition as reaction mixture after completion of oxidation of humic acid without any separation.
Claim 4 is Claim 5 of previous claim set. In present invention the product obtained from the oxidation reaction can be directly applied in laundry compositions without any further isolation/purification/separation steps. Hence, a more naturally ready biodegradable, biological builder that needs lesser processing prior to use in laundry composition is provided. Claim 4 denotes that oxidized humic acid or its salts are advantegous in terms of uncomplicated and economical obtainability.

5. A laundry composition according to claims 1 to 3, comprising addition of oxidized humic acid or its salts to the laundry composition as reaction mixture after completion of oxidation of humic acid and removal of reaction solvent.
Claim 5 takes place of Claim 6 of previous claim set. Claim 5 indicates that oxidized humic acid may also be used in laundry compositions after removing the reaction solvent from the oxidation reaction mixture. Solvent removed oxidized humic acid is especially useful for the solid form laundry compositions, and feasible in comparison to separated oxidized humic acid usage.

6. A laundry composition according to preceding claims, which further comprises a surfactant or surfactants, bleaching agents, hydrotropes, solvents, preservatives, antimicrobials, buffering agents, salts, fragrances, perfume, softening agents, foaming agent, foam reducing agent, opacifying agent, dye transfer inhibitor, redeposition inhibitor and enzymes.
Claim 8 and Claim 9 of previous claim set was united. Claim 6 underlines that oxidized humic acid or its salts are applicable and compatable with the common laundry ingredients.

7. A laundry composition according to preceding claims, comprising

a) from 1% to 35 % by weight of surfactant or surfactants

b) from 0.02% to 10% by weight of oxidized humic acid or its salts.

Claim 7 is reorganized form of claim 10 in previous claim set. Claim 7 indicates the necessity of surfactant existence in laundry compositions of the present invention since oxidized humic acid was not intented to perform as surfactant. Humic acid or its salts cannot be used in large amounts as surfactant due to slight coloring effects caused by coloring inherent to humic acid or its salts. The color inherent to humic acid or its salts are removed by oxidation step mostly so that usage in moderate amounts such as builder typical amounts is made possible. Therefore oxidized humic acid cannot replace surfactants in wide use range, and surfactants should be included to laundry compositions. "liquid" and "water" terms were removed from previous claim 10 to indicate not only liquid form but every form of laundry composition needs a co-existence of a surfactant or surfactants.

8. A liquid laundry composition according to claim 7, comprising

a) from 5% to 25% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 10% by weight of medium degree ethoxylated oleochemical alcohol

d) from 1% to 10 % by weight of diallyldimethyl ammonium chloride-propenamide copolymer

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

f) water

Claim 8 is Claim 13 of previous claim set. This claim indicates that oxidized humic acid is compatible with surfactants such as anionic surfactant like sodium lauryl ether sulfate and linear alkyl benzene sulfonic acid sodium salt, and other ingredients such as cationic surfactants or softener.

9. A liquid laundry composition according to claim 7, comprising

a) from 2% to 30% by weight of anionic surfactant

b)from 1% to 10% by weight of oleochemical alcohol

c) from 1% to 15 % by weight of cationic surfactant

d) from 0.02% to t 10% by weight of oxidized humic acid or its salts, and

e) water

wherein , oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.
Claim 9 is Claim 15 of previous claim set. This claim is about liquid laundry composition whereby oxidized humic acid is added to the composition without any separation step with reaction solvent. Thus, the composition is economically advantegous and favoured by its simplicity.

10. A liquid laundry composition according to claim 7, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1% to 5% by weight of enzyme

d) from 0.02% to 10% by weight of oxidized humic acid or its salts,

e) from 0.1% to 5% by weight of hydrotrope compound

f) water

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.
This claim is about liquid laundry composition whereby oxidized humic acid demonstrates compliance as builder with specific type igredients of laundry compositions such as anionic and nonionic surfactant, enzyme, hydrotrope compounds. This type of laundry formulation was indicated by Example 3 in description part.

11. A liquid laundry composition according to claim 7, comprising

a) from 3% to 15% by weight of sodium lauryl ether sulfate

b) from 3% to 15% by weight of linear alkyl benzene sulfonic acid sodium salt

c)from 1% to 20% by weight of ethoxylated oleochemical alcohol

d) from 0.1% to 5% by weight of enzyme

e) from 0.02% to 10% by weight of oxidized humic acid or its salts

f) from 0.1 % to 5% by weight of cumene sulfonate

g) water

This claim is about liquid laundry composition whereby oxidized humic acid demonstrates compliance as builder with specific type igredients of laundry compositions such as anionic and nonionic surfactant specifically as sodium lauryl ether sulfate and linear alkyl benzene sulfonic acid, enzyme, hydrotrope compounds to demonstrate the usefullness of oxidized humic acid as builder in such compositions. This type of laundry formulation was indicated by Example 3 in description part.

12. A solid laundry composition according to claim 1 to claim 7, wherein said solid composition may be in powder, granul, capsulated or tabletted form.
This claim indicates that oxidized humic acid can be present in solid form laundry compositions in powder, granul, capsule or tablet form as indicated in description part page 8 and page 9.

13. A solid laundry composition according to claim 12, comprising

a) from 3% to 25% by weight of anionic surfactant

b)from 1% to 20% by weight of nonionic surfactant

c) from 0.1 to 5% by weight of enzyme

d) from 0.02% to 10% by weight of oxidized humic acid or its salts

e) from 3% to 40% by weight of sodium carbonate

f) from 0.5 % to 5% by weight of defoamer compound

g)from 3% to 30% by weight of bleaching agent

h)from 1% to 15% by weight of silicate

wherein, oxidized humic acid is added to the laundry composition as reaction mixture after completion of oxidation of humic acid without removing reaction solvent.
This claim is about solid laundry composition whereby oxidized humic acid demonstrates compliance as builder with specific type igredients of laundry compositions such as anionic and nonionic surfactant, enzyme, sodium carbonate, polimerized silicate and bleaching agent. This type of laundry formulation was indicated by Example 2 in description part.
In addition to that this claim is about solid laundry composition whereby oxidized humic acid is added to the composition without any separation step with reaction solvent. Thus, the composition is economically advantegous and favoured by its simplicity.

14. A laundry composition according to preceding claims, wherein the laundry composition is in multicompartmental unit dose form such as tablet or pouch, and comprises at least two solid, liquid or gel form compartments.
Claim 14 shows that oxidized humic acid may be comprised by the multicompartmented tablet or multicompartmented water soluble pouches as indicated in description part page 8.

15. A laundry composition as claimed in any preceding claims, having application preferably on fabrics, clothes, carpets, woven or nonwoven type of textile.
Claim 15 indicates that compositions of present invention can be prefferably used on fabrics, clothes, carpets, woven or nonwoven type of textiles as indicated in description part page 8. "A cleaning composition" term here was changed with "A laundry composition" in order to maintain uniformity of new claim set.