Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38618—Protease or amylase in liquid compositions only
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/042—Acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2065—Polyhydric alcohols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2068—Ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2079—Monocarboxylic acids-salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/30—Amines; Substituted amines ; Quaternized amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/364—Organic compounds containing phosphorus containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38663—Stabilised liquid enzyme compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/143—Sulfonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

• the present invention refers to a detergent kit or a detergent dosing system comprising at least three different partial compositions A, B and C.
• the present invention further refers to three different liquid detergent compositions A, B and C representing partial compositions of a detergent kit or detergent dosing system.
• Composition A comprises at least one protease and optionally further enzymes only selected from the group of amylases and mannanases in combination with a high amount of anionic surfactants.
• Composition B comprises further enzymes, e.g. selected from the group comprising amylases, mannanases, lipases, pectinases and cellulases, but preferably no proteases.
• Composition C is the only composition of the detergent kit or detergent dosing system comprising an organic builder.
• the liquid detergent compositions A, B and C may be individually incorporated into one part of the detergent dosing system, wherein each part of the detergent kit or detergent dosing system comprises one of said liquid detergent compositions.
• the present invention refers to the use of liquid detergent compositions A, B, and/or C, or of a detergent kit or dosing system comprising said liquid detergent compositions A, B, and C, in a laundry washing process.
• detergent compositions comprise surfactants and enzymes in high concentrations.
• examples of such compositions are disclosed in DE 10 2012 211 028 A1 and WO 2004/008752 A1 . But said ingredients interfere with each other, as many enzymes are incompatible with particularly high concentrations of anionic surfactants like alkylbenzene sulfonic acids.
• enzymes are also not compatible with each other during storage, as e.g. proteases will decompose any enzymes, including themselves, by cleaving intramolecular peptide bonds.
• proteases will decompose any enzymes, including themselves, by cleaving intramolecular peptide bonds.
• Encapsulating, co-granulating or coating enzymes is however mainly useful for solid detergent compositions, as the protective shell would dissolve in a liquid detergent composition over time. Such a protection furthermore leads to the necessity of a further production step, which is undesired from an economical point of view.
• liquid detergent compositions to be dosed from them need to be storable for a longer time than conventional liquid detergents. This causes the necessity to provide detergents that are stable for such a time period, i.e. that do not gel, precipitate solids or considerably lose cleaning performance.
• the problem underlying the present invention therefore was to maintain and preferably improve the cleaning performance and stability of liquid detergent compositions over a prolonged time period in combination with providing a possibility to sufficiently soften the water used for washing without using higher amounts of detergent than necessary.
• a detergent kit or detergent dosing system comprising three separate compositions A, B and C, each of them independently representing a liquid detergent composition A, B and C, respectively, wherein the ingredients of the liquid detergent compositions A, B, C are composed different from each other.
• the detergent kit or detergent dosing system may comprise, apart from the partial compositions representing the above-described liquid detergent compositions A, B and C, one or more additional partial compositions, e.g. additional liquid (detergent) composition(s) like a fourth or fifth partial liquid (detergent) composition, which may individually provide e.g. bleach-active compounds, perfumes or fabric softeners.
• the present invention is therefore able to provide better storage stability, better washing results and overcomes ecological disadvantages of common detergents.
• Each partial composition may comprise at least one of the following ingredients, wherein some restrictions apply (see below for further details). Any relative amounts of components stated refer to the total weight of the respective liquid detergent composition A, B or C, in which said components are contained, unless otherwise stated.
• a (partial) liquid detergent composition according to the present invention may be defined as being "free of” a particular compound or ingredient, it may contain undesired trace amounts of said compound or ingredient. Said undesired trace amounts may be present in a (partial) liquid detergent composition according to the present invention in an amount of less than 0.2 wt.-%, preferably less than 0.1 wt.-%, more preferred 0.01 wt.-% based upon the total weight of the respective (partial) liquid detergent composition, most preferred a (partial) liquid detergent composition according to the present invention does not contain any undesired compounds or ingredients.
• a (partial) liquid detergent composition is described as "essentially consisting of" one or more ingredients or compounds, this means, that in this context the mentioned ingredients or compounds represent at least 95 wt.-% of the particular (partial) composition, preferably at least 96 wt.-%, more preferred at least 97 wt.-%, even more preferred at least 98 wt.-%, most preferred at least 99 wt.-%.
• anionic surfactants when referring to amounts of anionic surfactants throughout this document, in case of sulfonic acids and/or fatty acids the amounts given refer to their respective acid forms. When referring to anionic surfactants comprising sulfates, e.g. lauryl sulfates, laureth sulfates, (fatty) alcohol sulfates or ether sulfates, any amounts given refer to their respective sodium salts.
• enzymes are often used to aid the removal of stains. In most cases enzymes catalyze decomposition of the soiling and break it down into smaller pieces that have increased water solubility or are better dispersible in the washing liquor.
• Enzyme formulations useful for detergents can generally be in a liquid or solid form. Due to liquid enzyme formulations being easier to dissolve or emulsify in a liquid detergent composition, such formulations are preferred.
• Suitable enzymes to be used in a liquid detergent composition according to the present invention are for example, but not limited to, enzymes like proteases, esterases, lipases, amylases, mannanases, cellulases, pectinases and/or mixtures of these enzymes.
• Such enzymes support in removal of soil, like e.g. protein-, fat- or starch-containing stains as well as in the prevention of laundry graying and/or removal of graying from laundry.
• Particular cellulases are further able to increase laundry softness by removing pilling and/or microfibrils.
• Such cellulases are also known as anti-pilling cellulases.
• liquid detergent compositions may include any suitable enzyme supporting the cleaning performance or providing any benefit to the cleaned product.
• enzymes received from bacteria or fungi like Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens.
• Preferred proteases are of the subtilisin-type.
• Particularly suitable amylases comprise alpha-amylases, iso-amylases and/or pullulanases.
• Suitable enzymes of these types are e.g. provided by Novozymes A/S.
• the class of cellulases cellobiohydrolases, endoglucanases and beta-gluosidases or mixtures thereof are suitable enzymes for incorporation into a liquid detergent composition according to the present invention.
• Non-limiting examples comprise Celluclean 5000 L, available from Novozymes A/S, Biotouch FCL 75 and Biotouch FLX Zero, both available from AB Enzymes, and Revitalenz 200, available from DuPont.
• proteases A known disadvantage of proteases is, that these enzymes cleave not only peptide bonds present in their desired target molecules, i.e. protein molecules contained in soil, but also decompose enzymes, including other proteases. This leads to a loss of cleaning performance when the detergent is stored for a longer time period.
• the present invention overcomes this partial problem by providing enzymes particularly vulnerable to degradation from the proteases in separated partial liquid detergent compositions incorporating enzyme stabilizing compounds into the respective liquid detergent composition (see below for further details). Therefore, proteases are preferably contained in liquid detergent composition A, while the further enzyme-containing liquid detergent composition B is free of proteases.
• amylases and mannanases are less prone towards such protease-induced degradation
• amylases and/or mannanases may optionally be present together with proteases in liquid detergent composition A, while said composition is free from any enzymes different from proteases, amylases and/or mannanases. It is consequently particularly preferred to combine any enzymes different from proteases in liquid detergent composition B, while said liquid detergent composition B is free of proteases.
• Liquid detergent compositions A and B according to the present invention which comprise enzymes, further comprise two or more enzyme stabilizing compounds.
• Such compounds are able to decrease the protease activity. This effect is beneficial during storage, as enzymes are thereby protected from cleavage or degradation by the proteases or from self-degradation, defolding or interaction with enzymes being present in the liquid detergent compositions.
• a further task of enzyme stabilizing compounds is to prevent enzymes from aggregating, which might result in undesired precipitation of enzymes, thereby affecting homogeneity of the liquid detergent composition and available enzyme activity.
• suitable enzyme stabilizing compounds are polyols, particularly glycerol and 1,2-propylene glycol, benzamidine hydrochloride, mono-, di- or trialkanol amines such as mono-, di- or triethanol amine, boric acid, sodium borate (also known as borax), organoboronic acids, their salts or esters, acetic acid, polycarboxylic acids having 2 to 4 hydroxyl groups and 3 to 8 carbon atoms, and/or salts of the before-mentioned acids, in particular sodium, potassium and/or calcium salts.
• Such polycarboxylic acids are preferably selected from maleic acid, succinic acid, fumaric acid, tartaric acid and malic acid.
• a further enzyme stabilizing salt is calcium chloride.
• Formic acid and its salts e.g. sodium formate or potassium formate
• Formic acid and its salts are also able to prevent undesired precipitation of large amounts of enzymes, in particular of amylases.
• liquid detergent compositions according to the present invention comprise at least two, three or four enzyme stabilizing compounds selected from 1,2-propylene glycol, glycerol, boric acid, formic acid, ethanol amines, preferably monoethanol amine.
• the main function of builders is to soften the washing water, to provide pH regulation and a buffering capacity to the washing liquid and to have an antiredeposition or dispersing function in the cleaning composition.
• the physical properties of the cleaning composition are also depending at least partially on the builders that are used. For controlling the pH of the composition or wash liquor, as well as the mineral hardness of the liquor, inorganic as well as organic builders may be incorporated into the composition. In addition, these builders may assist in the removal of particulate soil.
• composition(s) may comprise an organic detergent builder, including polycarboxylate builders in the form of their acid or a salt, including alkali metal salts such as potassium, sodium and lithium salts.
• organic detergent builder including polycarboxylate builders in the form of their acid or a salt, including alkali metal salts such as potassium, sodium and lithium salts.
• the group of preferred builders includes in particular the citrates as well as the carbonates and the organic co-builders.
• citrate as used herein includes both citric acid as well as its salts, in particular its alkali metal, i.e. sodium, lithium and/or potassium, salts, wherein sodium citrate is particularly preferred.
• polycarboxylates/polycarboxylic acids may be used as organic co-builders. These classes of substances are described below.
• Suitable organic builder substances are, for example, the polycarboxylic acids usable in the form of the free acid and/or sodium salts thereof, "polycarboxylic acids” being understood as those carboxylic acids that carry more than one acid function. These are, for example, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for environmental reasons, as well as mixtures thereof.
• the free acids typically also possess, besides their builder effect, the property of an acidifying component, and thus also serve to establish a lower and/or milder pH for washing agents. To be recited in this context, in particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and/or any mixtures thereof are preferred.
• polymeric polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight from 500 to 70.000 g/mol or derivatives thereof.
• the molecular weight indicated for polymeric polycarboxylates are to be understood as weight-average molecular weights M w of the respective acid form that being determined in principle by means of gel permeation chromatography (GPC) coupled with a UV detector. The measurement may be performed against an external polyacrylic acid standard that yields realistic molecular weight values because of its structural similarity with the polymers being investigated.
• Polymers of the according Mw are offered on the market, wherein the Mw is announced by the retailer.
• Suitable polymers are, in particular, polyacrylates that preferably have a molecular weight from 2.000 to 20.000 g/mol.
• the short-chain polyacrylates which have molecular weights from 2.000 to 10.000 g/mol and particularly preferably from 3.000 to 5.000 g/mol, may be preferred because of their superior solubility.
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid that contain 50 to 90 wt.-% acrylic acid and 50 to 10 wt.-% maleic acid have been found particularly suitable.
• Their relative molecular weight, based on free acids is equal to in general 2.000 to 70.000 g/mol, preferably 20.000 to 50.000 g/mol, and in particular 30.000 to 40.000 g/mol.
• Suitable homo- or copolymeric acrylates comprise those sold under the trade name of Sokalan® by BASF, for example Sokalan CP5, Sokalan CP10 or Sokalan PA 25CI, without being limited thereto.
• Liquid detergent composition C preferably contains one or more builders selected from the builders described above, preferably a builder or a mixture of builders selected from the group of organic builders.
• organic builders citric acid and/or salts thereof as well as polymeric builder compounds, such as water-soluble homopolymers comprising acrylic and/or methacrylic monomers, copolymers of two or more monomers, wherein at least one monomer is selected from the group comprising acrylic acid, methacrylic acid and/or maleic acid, mixtures thereof and/or salts thereof, are particularly preferred.
• composition C comprises at least a citrate, more preferred sodium citrate as one builder.
• Liquid detergent compositions A, B and any further liquid detergent compositions are free of builders selected from citric acid and/or salts thereof and are preferably free of any builders.
• builders as described above are distinguished from complexing or sequestering agents as described below.
• a further optional, but preferred ingredient of the liquid detergent compositions according to the present invention is at least one complexing (or sequestering) agent.
• Complexing agents are commonly used to support the performance of the builders.
• a function of complexing agents is to capture trace metal ions like Cu(II), Fe(II), Fe(III), Mn(II), Cd(II), Co(II), Cr(III), Hg(II), Ni(II), Pb(II), Pd(II), Zn(II), Ca(II), Mg(II).
• These ions can interfere with or disturb certain ingredients of the detergent compositions in the washing machine, like e.g. denaturate or precipitate enzymes.
• Complexing agent(s) suitable to be used in detergent compositions according to the present invention include, but are not limited to, S,S -ethylenediamine- N,N'- disuccinic acid (S,S-EDDS), ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), ethanol diglycine (EDG), imino disuccinic acid (IDS), methylglycine diacetic acid (MGDA), diethylene triamine pentaacetic acid (DTPA), ethylene diamine dihydroxyphenyl acetic acid (EDDHA), N -(hydroxyethyl) ethylenediamine triacetic acid (HEDTA), hydroxyethylidene-1,1-diphosphonic acid (HEDP), phytic acid, diethylene triamine (DETA), triethylene tetramine (TETA), tetraethylene pentamine (TEPA), aminoethyl ethanolamine (AEEA), glutamic acid N,N -
• phosphonates are preferred complexing agents.
• Useful phosphonates encompass a number of different compounds such as, for example, 1-hydroxyethane-1,1-diphosphonic acid, diethylenetriamine penta (methylene phosphonic acid) (DTPMP), ethylenediamine tetramethylene phosphonate (EDTMP), as well as higher homologs thereof.
• DTPMP diethylenetriamine penta
• EDTMP ethylenediamine tetramethylene phosphonate
• the aminoalkane phosphonates EDTMP and DTPMP moreover possess a pronounced ability to bind heavy metals.
• MGDA and/or salts thereof commercially available for example from BASF under the trade name of Trilon® M, GLDA, phosphonates, in particular DTPMP, and/or salts thereof are particularly preferred.
• Complexing agents can generally be added to any of the liquid detergent compositions in acid form, in a neutralized or in a partly neutralized form.
• the term (partly) neutralized in this context refers to complexing agents being (partly) present in form of their salts.
• ammonium or alkali metal salts, like sodium, potassium and lithium salts, of the above-mentioned complexing agents are preferred.
• phosphonates are used preferably in the form of the neutrally reacting sodium salts, e.g. as a hexasodium salt of EDTMP or as a hepta- or octasodium salt of DTPMP, respectively.
• At least some of the partial liquid detergent compositions of the present invention comprise one or more surfactants.
• Particularly at least compositions A and B comprise at least one type of surfactant.
• Said surfactants may be selected from anionic, non-ionic, cationic or amphoteric surfactants, however, anionic and/or nonionic surfactants are preferred.
• surfactants are changing the surface tension, dispersing, foam controlling and surface modification.
• Anionic surfactants suitable to be used in detergents, in particular in combination with enzymes are well known in the art and comprise alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl carboxylates and salts thereof, for example alkyl benzene sulfonates, alkyl or alkenyl sulfonates, fatty alcohol sulfates and ethoxylated fatty alcohol sulfates.
• sulfate sulfonate
• carboxylate as used in this context may throughout the whole content of the description refer to the corresponding acid form, salts thereof and/or mixtures of acid forms and salts. Any organic or inorganic counterions known in the art may be used to form such salts, however, sodium, lithium, potassium and ammonium salts are preferred, whereas sodium salts are particularly preferred.
• Particularly suitable anionic surfactants used in liquid detergent compositions are alkylbenzene sulfonates, alkyl sulfonates and salts thereof.
• Suitable anionic alkylbenzene sulfonic or alkyl sulfonic acid surfactants include in particular C 5 -C 20 , preferably C 10 -C 16 , more preferably C 11 -C 13 alkylbenzene sulfonates, e.g. dodecylbenzene sulfonate (salts), linear alkylbenzene sulfonates (LAS), alkylester sulfonates, primary or secondary alkene sulfonates, sulfonated polycarboxylic acids and any mixtures thereof.
• Alkylbenzene sulfonates or alkylether sulfates comprising a branched alkyl group may be used as well.
• alkyl or alkenyl sulfates are alkali, preferably sodium, salts of sulfuric acid esters of fatty alcohols with 10 to 18 carbon atoms, e.g. coco or tallow fatty alcohols, lauryl, cetyl, stearyl or myristyl alcohols as well as primary or secondary oxo alcohols with 8 to 20 carbon atoms.
• Preferred alkyl sulfonates are C 10 -C 18 alkyl sulfonates, more preferred C14-C17 alkyl sulfonates, in particular C14-C17 secondary alkyl sulfonates.
• a further type of suitable anionic surfactants are fatty alcohol sulfates, in particular those with C 10 -C 18 alkyl chains, preferably C 12 -C 18 alkyl chains.
• sulfates of linear or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide (EO) per mole of alcohol like 2-methyl C 9 -C 11 alcohols with an average of 3.5 EO or C 12 -C 18 fatty alcohols with 1-4 EO are suitable.
• EO ethylene oxide
• One particular example is sodium laureth sulfate.
• surfactants containing ethoxylated alcohols may comprise different EO amounts
• the cited degrees of ethoxylation constitute statistically average values that can be a whole or a fractional number for a specific product.
• surfactants for use in the present compositions are non-ionic surfactants.
• Suitable nonionic surfactants are alkoxylated, advantageously ethoxylated, fatty alcohols.
• Examples are primary alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched residues in the mixture, as usually present in oxo alcohol residues.
• EO ethylene oxide
• the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 alcohols with 3 EO and C 12 -C 18 alcohols with 5 EO.
• the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohols with 14 EO to 100 EO, like 14 EO, 25 EO, 30 EO, 40 EO or 100 EO.
• nonionic surfactants and alkyl glycosides of the general formula RO(G)x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position, aliphatic residue having 8 to 22, preferably 12 to 18 carbon atoms, and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any integer or fractional number between 1 and 10; preferably x is 1.2 to 1.4.
• nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
• Nonionic surfactants of the amine oxide type for example N -cocoalkyl- N,N- dimethylamine oxide and N -tallowalkyl- N,N -dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula R-C(O)-N(R 1 )[Z], in which R-C(O) is an aliphatic acyl residue having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl residue having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl residue having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula R-C(O)-N(R 1 OR 2 )[Z], in which R is a linear or branched alkyl or alkenyl residue having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl residue or an aryl residue having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl residue or an aryl residue or a Oxy-alkyl residue having 1 to 8 carbon atoms, wherein C1 is 4-alkyl or phenyl residues are preferred and [Z] is a linear polyhydroxyalkyl residue whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N -alkoxy- or N -aryloxy-substituted compounds can be converted into the respective polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• nonionic surfactants to be used within a liquid detergent composition according to the present invention are surfactants solid at room temperature and are selected from the group of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• a preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16 -C 20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide (EO).
• C 16 -C 20 alcohol a straight chain fatty alcohol having 16 to 20 carbon atoms
• EO ethylene oxide
• Nonionic surfactants solid at room temperature may additionally have propylene oxide units in the molecule, such nonionic surfactants are ethoxylated monohydroxy alkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
• nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by wt.-% of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
• Nonionic surfactants of the formula R 1 O[CH 2 CH(CH 3 )O] x CH 2 CH 2 O] y [CH 2 CH(OH)R 2 ], in which R 1 is a linear or branched aliphatic hydrocarbon residue having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon residue having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15, may also be used.
• nonionic surfactants are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 , where R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl residue, x has a value of 1 to 30, k and j have values of 1 to 12, preferably between 1 and 5.
• R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues having 6 to 22 carbon atoms, with residues having 8 to 18 carbon atoms being preferred.
• R 3 H, -CH 3 or -CH 2 CH 3 are preferred.
• Preferred values for x are in the range from 1 to 20, more preferred from 6 to 15.
• the liquid detergent composition according to the present invention and all its partial compositions can be aqueous or non-aqueous compositions, or are compositions comprising both organic solvents and water.
• all of the compositions A, B, C, D and E comprise at least any amount of water.
• Said compositions may apart from being solutions also be emulsions or dispersions.
• all incorporated ingredients are fully dissolved in liquid detergent compositions according to the present invention.
• Suitable organic solvents to be incorporated into liquid detergent compositions according to the present invention comprise ethers, alcohols, diols, polyols, ketones, amides and/or esters.
• Preferred solvents are monomeric polar compounds like methanol, ethanol, 1-propanol, 2-propanol, propylene carbonate, acetone, acetonyl acetone, diacetone alcohol, ethyl acetate, ethylene glycol, propylene glycol, glycerol, diethylene glycol, diproplylene glycol monomethyl ether and/or mixtures thereof.
• the different partial liquid detergent compositions may possess equal or different viscosities and pH values.
• Typical viscosities of partial liquid detergent compositions A, B and/or C may range from0-500, preferably 50-200, measured at 20 °C with a Brookfield viscosimeter at 12 rpm using spindle 1.
• Typical pH values of liquid detergent compositions A, B and/or C may range from 6-10, preferably 7-9.
• At least one of the liquid detergent compositions A, B and/or C according to the present invention may additionally comprise one or more "performance polymer(s)".
• performance polymer(s) enhance removal of particularly persistent stains, e.g. such occurring from grass, clay or certain types of fruit, e.g. red berries, and further prevent soil redeposition and graying of textile fibers.
• performance polymers are therefore also suitable to substitute partial amounts of surfactants.
• a non-limiting example of a performance polymer is an ethoxylated polyethylene imine, e.g. Sokalan® HP 20, commercially available from BASF.
• dye molecules may be washed off from colored fibers. This particularly happens at elevated temperatures or in presence of high amounts of surfactants. Redeposition of such washed off dyes on other pieces of laundry may result in undesired color changes of the washed laundry.
• a dye transfer inhibitor is able to suppress or avoid said effect.
• Dye transfer inhibitor(s) may be selected from polymers.
• Polymeric dye transfer inhibitors react or form complexes with dye molecules, thereby increasing water solubility and preventing redeposition of the dyes.
• a nonlimiting example of such a polymeric dye transfer inhibitor is a vinylpyrrolidone / vinylimidazole copolymer, e.g. Sokalan® HP 56 BM commercially available from BASF..
• At least one of the liquid detergent compositions A, B and/or C, preferably liquid detergent compositions A and/or B, according to the present invention may additionally comprise one or more dye transfer inhibitors.
• optical brightener is a fluorescent compound having an absorption maximum in the UV range (approx. 290 - 400 nm) and re-emit in the blue region of the visible spectrum. Such compounds normally used make washed laundry to look cleaner and brighter in order to make the washed laundry appear more appealing to the consumer. Laundry washed without an optical brightener looks slightly yellowish, while the optical brightener overcomes this problem by compensating the deficit in blue and purple light reflected by the material.
• optical brighteners are condensed aromatic/heteroaromatic compounds, including condensed thiazoles, pyrazoles, oxadiazoles and triazines, and stilbene or biphenyl derivatives.
• Common optical brighteners used in laundry detergents are for example DAS1 (Disodium 4,4'-bis[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino]-stilbene-2,2-disulfonate) and DSBP (Disodium 4,4'-bis(2-sulfostyryl)-biphenyl).
• bleaching agents may be added to the washing liquor.
• Such bleaching agents contain or produce, either by means of a chemical reaction or by release, oxidizing agents such as hydrogen peroxide or a peracid when brought into contact with the washing liquor. Said oxidizing agents react with particular molecules present in bleachable stains, thus increasing water solubility and decomposing chromophores present in said stain molecules.
• Bleaching agents suitable for use in a composition according to the present invention include, but are not limited to, active chlorine compounds, inorganic peroxygen compounds and organic peracids. Examples are sodium percarbonate, sodium perborate monohydrate, sodium perborate tetrahydrate, hydrogen peroxide, hydrogen peroxide-based compounds, persulfates, peroxomonosulphate, peroxodisulphate, ⁇ -phthalimido-peroxy-caproic acid, benzoyl peroxide as well as mixtures thereof.
• the detergent kit or detergent dosing system may optionally comprise a fourth partial liquid detergent composition D1 comprising bleaching agent(s) and a fifth partial liquid detergent composition D2 comprising bleach activators and/or bleach catalysts as described in further detail below.
• bleach activator any compound is meant, which is able to provide the possibility to use a comparatively low temperature to achieve the desired bleaching performance when inorganic peroxygen based bleaching agents are applied.
• a bleach activator reacts with the peroxygen to form an organic peracid.
• these peracids can have a hydrophobic or a hydrophilic character.
• Suitable bleach activators yield peracids, particularly those with 1 to 10 carbon atoms, preferably 2-4 carbon atoms, and/or (substituted) perbenzoic acids, under perhydrolysis conditions, i.e. when reacting with the bleaching agent.
• Suitable bleach activators are compounds carrying O- and/or N -acyl groups comprising the above-mentioned ranges of carbon atoms and/or (substituted) benzoyl groups.
• multiply acylated alkylene diamines preferably tetraacetylene diamine (TAED), acylated triazine derivatives, preferably 1,5- diacetyl 2,4-hexahydro- 1,3,5-triazine (DADHT), N -acyl imides, preferably N -nonanoyl succinimide (NOSI).
• TAED tetraacetylene diamine
• DADHT 1,5- diacetyl 2,4-hexahydro- 1,3,5-triazine
• NOSI N -nonanoyl succinimide
• bleach activators include, but are not limited to, sodium nonanoyloxybenzene sulfonate (NOBS), acetyl caprolactone, N -methyl morpholinium acetonitrile and salts thereof, sodium 4-(2-decanoyl-oxyethoxycarbonyloxy)benzenesulfonate (DECOBS) and salts thereof, lauryloxybenzyl sulfonate (LOBS), iso-lauryloxybenzyl sulfonate (I-LOBS), N-methylmorpholinum-acetonitrile (MMA), pentaacetyl glucose, nitrile quats, benzoyl caprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-clorobenzoylcaprolactam, benzoyloxybenzyl sulfonate (BOBS), phenyl benzoate (PhBz), decanoyloxybenzyl sulfonate (C10-
• a bleach catalyst may be incorporated into a composition according to the present invention.
• Suitable bleach catalysts comprise metal containing bleach catalyst that are selected from bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes.
• metal containing bleach catalyst such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes.
• Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, as well as cobalt-, iron-, copper- and ruthenium-ammine complexes may also be employed as the bleach catalysts.
• Such catalysts are broadly described in the state of the art and well known by skilled artisans.
• Complexes of manganese in the valence state II, III, IV or V which preferably comprise one or a plurality of macrocyclic ligands with the donor functions N, NR, PR, O and/or S are particularly preferably employed.
• Ligands having nitrogen donor functions are preferably employed.
• the at least one bleach catalyst from such having a group 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN) 1,2,4,7,-tetramethyl-1,4,7-triazacyclononane and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN) as the macromolecular ligands.
• Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
• TACN 1,4,7-triazacyclononane
• TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
• Preferred manganese complexes are for example [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ](ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 2 ( ⁇ -OAc) 1 (TACN) 2 ](BPh 4 ) 2 , [Mn IV 4( ⁇ -O) 6 (TACN) 4 ](ClO 4 ) 4 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAC) 2 (Me-TACN) 2 ](ClO 4 ) 2 , [Mn III mn IV ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ](ClO 4 ) 3 , [Mn IV 2 ( ⁇ -Oh) 3 (Me-TACN) 2 ](PF 6 ) 2 (MnTACN), [Mn IV 2 ( ⁇ -O) 3 (Me/Me-TACN) 2 ](PF 6 ) 2 (O
• the detergent kit or detergent dosing system according to the present invention may optionally further comprise a sixth partial composition, represented by composition E.
• Said composition is related to add fabric softeners when performing the last rinse of the washed laundry.
• Machine washing puts great mechanical stress on laundry, particularly natural fibers such as cotton and wool.
• the fibers at the fabric surface are squashed and frayed, and this condition hardens while drying the laundry in air, giving the laundry a harsh feel, which is undesired by the consumer.
• Adding a liquid fabric softener to the final rinse of the washing cycle results in laundry that feels softer.
• Liquid detergent compositions according to the present invention may further comprise other ingredients allowing any desired performance as known by the skilled artisan without limiting the invention.
• Optional ingredients of the present liquid detergent compositions comprise for example dyes and/or perfumes.
• a dye is used to color the detergent composition. This might render the product more attractive to the consumer.
• a perfume is added to the cleaning composition to improve the sensorial properties of the composition or of the laundry after washing.
• ingredients may also include thickeners, preservatives, UV-absorbers, foam inhibitors, soil repellents, color transfer inhibitors, corrosion inhibitors and/or solvents, without being limited thereto.
• the first partial composition of the detergent kit or detergent dosing system is represented by liquid detergent composition A.
• Said liquid detergent composition A comprises at least one protease, optionally at least one amylase and/or mannanase, two or more enzyme stabilizing compounds selected from the group comprising propylene glycol, boric acid, formic acid and ethanol amines, preferably monoethanol amine, and at least one anionic surfactant comprising alkylbenzene sulfonic acids and/or salts thereof, wherein alkylbenzene sulfonic acid and/or salts thereof are present in an amount of at least 27.5 wt.-%, preferably at least 29 wt.-%, more preferred at least 29.5 wt.-% of the liquid detergent composition A, wherein liquid detergent composition A is free of builders selected from the group of citric acid and/or salts thereof and enzymes different from proteases, amylases or mannanases.
• composition A comprises essentially the whole content of protease enzyme of the provided liquid detergent and a high amount of alkylbenzene sulfonic acid (salts).
• Said composition is therefore related to providing a high amount of anionic surfactants, particularly alkylbenzene sulfonic acids, to improve cleaning performance. It is further related to providing proteases in a particularly high amount in combination with at least two enzyme-stabilizing compounds.
• Particularly suitable anionic alkylbenzene sulfonic acids are C 5 -C 20 , preferably C 10 -C 16 , more preferably C 11 -C 13 , most preferred C 12 (dodecyl) alkylbenzene sulfonic acids.
• the alkyl groups present in said alkylbenzene sulfonic acids can be linear and/or branched alkyl groups.
• Such alkylbenzene sulfonic acid (salts) may be present in composition A in a minimum amount of at least 27.5 wt.-%, preferably at least 29 wt.-%, more preferred at least 29.5 wt.-% of liquid detergent composition A and in a maximum amount of up to 50 wt.-%, preferably up to 45 wt.-%, more preferred 40 wt.-%, most preferred 36 wt.-% of liquid detergent composition A.
• Liquid detergent composition A may additionally comprise one or more of the above-described further anionic surfactants. These are preferably selected from C 10 -C 20 , more preferred C 14 -C 18 , fatty acids, salts thereof and alkyl polyether sulfates, most preferred from sodium laureth sulfate.
• the total amount of anionic surfactants present in composition A may be between 38 wt.-% and 60 wt.-%, preferably between 39.5 wt.-% and 55 wt.-%, more preferred between 40.5 wt.-% and 50 wt.-% of liquid detergent composition A.
• Liquid detergent composition A only comprises enzymes compatible with high amounts of alkylbenzene sulfonic acids and/or their salts. It therefore comprises any protease and optionally further only enzymes selected from amylase(s) and/or mannanases(s). Liquid detergent composition A is however free of enzymes different from proteases, amylases and mannanases. Due to not comprising enzymes, which are particularly prone to protease degradation, said composition A contains proteases and, if present, amylases and/or mannanases in a particularly high amount.
• Protease(s) may be present in liquid detergent composition A in amounts (of the active enzyme) of between 0.08 wt.-% and 1 wt.-%, preferably 0.1 wt.-% to 0.5 wt.-%, more preferred 0.13 wt.-% to 0.25 wt.-% of liquid detergent composition A. If present, the amount of amylase(s) is between 0.008 wt.-% and 0.
• liquid detergent composition A 5 wt.-%, preferably 0.01 wt.-% to 0.25 wt.-%, more preferred 0.0125 to 0.1 wt.-% of liquid detergent composition A and, if present, the amount of mannanases(s) is between 0.001 wt.-% and 0.02 wt.-%, preferably 0.0012 wt.-% to 0.018 wt.-%, more preferred 0.00125 to 0.016 wt.-%, most preferred 0.0013 wt.-% to 0.014 wt.-% of liquid detergent composition A.
• Activity of the above-mentioned enzymes contained in liquid detergent composition A during storage is decreased by the presence of at least two enzyme stabilizing compounds to avoid undesired enzyme degradation over a longer time period.
• enzyme-stabilizing compounds are selected from the group comprising propylene glycol, glycerol, boric acid, acetic acid, ethanol amines, preferably monoethanol amine, calcium chloride.
• Other optional enzyme stabilizing compounds are acetic acid and polycarboxylic acids having 2 to 4 hydroxyl groups and 3 to 8 carbon atoms as well as their salts, particularly sodium, potassium and/or calcium salts.
• Such polycarboxylic acids are preferably selected from maleic acid, succinic acid, fumaric acid, tartaric acid and malic acid.
• Enzyme stabilizing compounds may be present in liquid detergent composition A in a total amount between 8 wt.-% to 30 wt.-%, preferably 12 wt.-% to 27 wt.-%, more preferred 15 wt.-% to 25 wt.-% of liquid detergent composition A.
• amylase(s) is/are present in liquid detergent composition A
• at least formic acid is present as an enzyme stabilizing compound, alternatively formic acid or boric acid in combination with monoethanol amine are particularly preferred.
• liquid detergent composition A is furthermore free of builders comprising citric acid and/or salts thereof and is preferably free of any builder(s). Such builders could otherwise contribute to enzyme unfolding, degradation or deactivation. What is meant by "builders" in this context is defined above.
• Nonionic surfactants are selected from any nonionic surfactants as defined in this disclosure.
• Preferred are alkoxylated, advantageously ethoxylated, in particular primary, C 8 -C 18 alcohols with 1-12 EO, in which the alcohol residue is linear or preferably methyl-branched in the 2-position or contains linear and methyl-branched residues in the mixture.
• alcohol ethoxylates with linear residues of C 12 -C 18 alcohols of natural origin e.g.
• coconut, palm, tallow or oleyl alcohol with 2 to 8 EO, preferably C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and/or mixtures thereof, more preferred mixtures of C 12 -C 14 alcohols with 3 EO and C 12 -C 18 alcohols with 5 or 7 EO, most preferred C 12 -C 18 ethoxylated alcohols with 7 EO.
• Nonionic surfactants may be present in a maximum amount of 25 wt.-%, preferably and 22 wt.-%, more preferred 20 wt.-% of composition A and in a minimum amount of 5 wt.-%, preferably 10 wt.-%, more preferred 15 wt.-% of liquid detergent composition A.
• the ratio of anionic surfactants to nonionic surfactants in liquid detergent composition A may be between 5 to 1 and 1 to 1, preferably between 4 to 1 and 1.5 to 1, more preferred 3.5 to 1 and 1.7 to 1, most preferred 2.15 to 1 and 1.8 to 1, based on weight-percentage amounts of liquid detergent composition A.
• Additional optional, but preferred, ingredients of liquid detergent composition A comprise further at least one performance polymer and/or soil release polymer.
• Such polymers act as supporting agents in order to improve the removal of particular types of soil, like e.g. grass, fruit and clay, prevent graying of fibers and prevent redeposition of soil during the washing cycle.
• Performance polymers are preferably selected from ethoxylated polyethyleneimines, while soil release polymers are preferably selected from esters of terephthalic acids.
• Said performance polymer or said soil release polymer may individually be present in liquid detergent composition A in an amount between 0.5 wt.-% and 5 wt.-%, preferably 1 wt.-% to 4 wt.-%, more preferred 1.3 wt.-% to 3.5 wt.-%, most preferred 1.6 wt.-% to 3.2 wt.-% of liquid detergent composition A.
• Additional components which may preferably be incorporated into liquid detergent composition A comprise organic solvents as described above, which are preferably selected from the group of linear and/or branched aliphatic mono-, di- and/or tri-alcohols, preferably comprising 1-4 carbon atoms, more preferably ethanol, mono propylene glycol and/or glycerol, pH regulating compounds, e.g. NaOH, HCI or buffer compounds, and water.
• organic solvents as described above, which are preferably selected from the group of linear and/or branched aliphatic mono-, di- and/or tri-alcohols, preferably comprising 1-4 carbon atoms, more preferably ethanol, mono propylene glycol and/or glycerol, pH regulating compounds, e.g. NaOH, HCI or buffer compounds, and water.
• liquid detergent composition A is essentially consisting of the above-mentioned ingredients, namely surfactants, organic solvent(s), water, enzyme(s), enzyme stabilizing compounds, soil release and/or performance polymer, and pH regulator(s).
• composition of liquid detergent composition A is as follows: Component Amount [wt.-%] enzyme stabilizing compounds 12 - 25 alkylbenzene sulfonic acid(s) (anionic surfactant) 25 - 35 (salts of) fatty acids (anionic surfactant) 1 - 5 sulfates of ethoxylated fatty alcohols (anionic surfactant) 5 - 10 ethoxylated alcohols (nonionic surfactant) 15 - 25 pH regulator(s) 4.5 - 11 protease(s) (active content) 0.08 - 0.25 amylase(s) (active content) 0 - 0.5 performance polymer 0 - 5 solvents (water, ethanol, propylene glycol) to balance
• liquid detergent composition A The aspects of liquid detergent composition A are:
• the second partial composition of the detergent kit or dosing system is represented by liquid detergent composition B.
• Said liquid detergent composition B comprises two or more enzymes (except protease(s)), at least one anionic surfactant selected from alkylbenzene sulfonic acid (salts), ethoxylated fatty alcohol sulfates, fatty alcohol sulfates, and/or alkyl sulfonates in an amount between 5 wt.-% and 30 wt.-%, preferably between 12 wt.-% and 25 wt.-%, more preferred between 16 and 22 wt.-% of liquid detergent composition B, at least one enzyme stabilizing compound comprising formic acid and optionally an enzyme stabilizing compound selected from ethanol amines, preferably monoethanol amine, propylene glycol and/or glycerol, wherein liquid detergent composition B is free of citric acid and/or salts thereof and proteases.
• anionic surfactant selected from alkylbenzene sulfonic acid (salts), ethoxylated fatty alcohol sulfates
• Composition B is related to providing a high amount of anionic surfactants, while the amount of alkylbenzene sulfonic acids and/or salts thereof is significantly reduced in this partial composition B, compared to partial composition A, to maintain enzyme-compatibility.
• Said composition B comprises instead a mixture of anionic surfactants additionally to, or instead of, alkylbenzene sulfonic acids and/or salts thereof. It is further related to providing enzymes different from proteases in combination with at least two enzyme-stabilizing compounds.
• composition B comprises alkyl sulfonates, fatty alcohol sulfates and/or ethoxylated fatty alcohol sulfates as anionic surfactants, but no alkyl benzene sulfonates.
• one or more fatty acids may be present as optional anionic surfactants.
• Preferred alkyl sulfonates are C 10 -C 18 , more preferred C 14 -C 17 alkyl sulfonates.
• Alkylbenzene sulfonic acids or salts thereof are preferably selected from C 10 -C 15 alkylbenzene sulfonic acids or salts thereof, more preferred C 11 -C 14 alkylbenzene sulfonic acids or salts thereof, most preferred from dodecylbenzene sulfonic acid or salts thereof and contain a linear or a branched alkyl group.
• Liquid detergent composition B further comprises additional anionic surfactants which are different from alkylbenzene sulfonic acid (salts) to compensate for the reduced amount of said surfactants.
• additional anionic surfactants are selected from ethoxylated fatty alcohol sulfates, fatty alcohol sulfates and alkyl sulfates.
• Liquid detergent composition B may be free of alkylbenzene sulfonic acid (salts) and may further optionally comprise fatty acid (salts) as anionic surfactants.
• Anionic surfactants different from alkylbenzene sulfonic acid are preferably selected from the group of sodium laureth sulfate, sodium salts of fatty alcohol sulfates with 12 to 18 carbon atoms, palm kernel acid, salts of palm kernel acid and mixtures thereof.
• sodium, potassium and/or monoethanol ammonium salts are preferred, in particular sodium salts.
• Anionic surfactants are preferably present in a total amount of between 15 wt.-% and 40 wt.-%, preferably between 16 wt.-% and 35 wt.-%, more preferred between 17 wt.-% and 32.5 wt.-%, most preferred between 18 wt.-% and 30 wt.-% of the liquid detergent composition B.
• This value refers to the total amount of any anionic surfactant as defined above, including optional fatty acid (salts).
• Suitable enzymes to be used within liquid detergent composition B are all enzymes as defined above, with the exception of proteases, which liquid detergent composition B is free of.
• Said composition comprises at least one enzyme selected from mannanases, pectinases, lipases, amylases and cellulases, wherein cellulases may also comprise any anti-pilling cellulases.
• Mannanases may be present in an amount between 0.001 wt.-% and 0.1 wt.-%, preferably 0.0012 wt.-% to 0.05 wt.-%, more preferred 0.00125 to 0.025 wt.-%, most preferred 0.0013 wt.-% to 0.002 wt.-% of liquid detergent composition B.
• Pectinases may be present in an amount between 0.001 wt.-% and 0.1 wt.-%, preferably between 0.003 wt.-% and 0.05 wt.-%, more preferred between 0.004 wt.-% and 0.01 wt.-% of liquid detergent composition B.
• Lipases may be present in an amount between 0.001 wt.-% and 0.1 wt.-%, preferably between 0.01 wt.-% and 0.08 wt.-%, more preferred between 0.015 wt.-% and 0.07 wt.-% of liquid detergent composition B.
• Amylases may be present in an amount between 0.008 wt.-% and 0.1 wt.-%, preferably between 0.01 wt.-% and 0.05 wt.-%, more preferred between 0.0125 wt.-% and 0.015 wt.-% of liquid detergent composition B.
• Cellulases may be present in an amount between 0.001 wt.-% and 0.1 wt.-%, preferably between 0.005 wt.-% and 0.05 wt.-%, more preferred between 0.01 wt.-% and 0.02 wt.-% of liquid detergent composition B.
• composition B comprises at least two, more preferred at least three of the above-mentioned enzymes.
• the total amount of enzymes being present in liquid detergent composition B is between 0.021 wt.-% and 0.5 wt.-%, preferably 0.025 wt.-% to 0.25 wt.-%, more preferred 0.03 wt.-% to 0.1 wt.-%, most preferred 0.04 wt.-% to 0.05 wt.-% of liquid detergent composition B.
• Liquid detergent composition B therefore comprises at least formic acid as an enzyme stabilizing compound, preferably in an amount between 0.2 wt.-% and 1.5 wt.-%, more preferred between 0.4 wt.-% and 1.2 wt.-%, most preferred between 0.5 wt.-% and 1 wt.-%, of liquid detergent composition B, and optionally a further enzyme stabilizing compound selected from ethanol amines, preferably monoethanol amine, propylene glycol, glycerol and/or calcium chloride.
• enzyme stabilizing compounds are acetic acid and polycarboxylic acids having 2 to 4 hydroxyl groups and 3 to 8 carbon atoms as well as their salts, particularly sodium, potassium and/or calcium salts.
• polycarboxylic acids are preferably selected from maleic acid, succinic acid, fumaric acid, tartaric acid and malic acid
• enzyme stabilizing compounds may be present in liquid detergent composition B in a total amount between 5 wt.-% to 25 wt.-%, preferably 8 wt.-% to 20 wt.-%, more preferred 10 wt.-% to 18 wt.-% of liquid detergent composition B.
• liquid detergent composition B is furthermore free of citric acid and/or salts thereof and is preferably free of any builders as defined above. Such said substances could otherwise contribute to enzyme unfolding, degradation or deactivation.
• Nonionic surfactants are selected from any nonionic surfactants defined in this disclosure.
• Preferred are alkoxylated, advantageously ethoxylated, in particular primary, C 8 -C 18 alcohols with 1-12 EO, in which the alcohol residue is linear or preferably methyl-branched in the 2-position or contains linear and methyl-branched residues in the mixture.
• alcohol ethoxylates with linear residues of C 12 -C 18 alcohols of natural origin, e.g.
• coconut, palm, tallow or oleyl alcohol with 2 to 8 EO, preferably C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and/or mixtures thereof, more preferred mixtures of C 12 -C 14 alcohols with 3 EO and C 12 -C 18 alcohols with 5 or 7 EO, most preferred C 12 -C 18 ethoxylated alcohols with 7 EO.
• Such nonionic surfactants may be present in an amount between 5 and 30 wt.-%, preferably between 10 wt.-% and 25 wt.-%, more preferred between 15 wt.-% and 23 wt.-%, most preferred between 18 wt.-% and 22 wt.-% of liquid detergent composition B.
• the ratio of anionic surfactants to nonionic surfactants in liquid detergent composition B may be between 1.9 to 1 and 1 to 1, preferably between 1.8 to 1 and 1.1 to 1, more preferred between 1.75 to 1 and 1.25 to 1, most preferred between 1.65 to 1 and 1.35 to 1, based on weight-percentage amounts of liquid detergent composition B.
• Additional components which may preferably be incorporated into liquid detergent composition B comprise organic solvents as described above, which are preferably selected from the group of linear and/or branched aliphatic mono- and/or di-alcohols, preferably comprising 1-4 carbon atoms, more preferably ethanol, pH regulating compounds, e.g. NaOH, HCI or buffer compounds, and water.
• organic solvents as described above, which are preferably selected from the group of linear and/or branched aliphatic mono- and/or di-alcohols, preferably comprising 1-4 carbon atoms, more preferably ethanol, pH regulating compounds, e.g. NaOH, HCI or buffer compounds, and water.
• chelating agents as defined above, preferably a phosphonate, more preferred diethylenetriamine penta(methylene phosphonic acid) (DTPMP), and/or salts thereof.
• DTPMP diethylenetriamine penta(methylene phosphonic acid)
• liquid detergent composition B may further comprise a dye transfer inhibitor, which is selected from polymeric compounds, and is preferably a vinylpyrrolidone / vinyl imidazole copolymer.
• Said inhibitor may be present in liquid detergent composition B in amounts between 0.1 wt.-% and 5 wt.-%, preferably 0.3 wt.-% to 2 wt.-%, more preferred 0.4 wt.-% to 1 wt.-%, most preferred 0.5 wt.-% to 0.8 wt.-% of liquid detergent composition B.
• the liquid detergent composition B is essentially consisting of the above-mentioned ingredients, namely surfactants, organic solvent(s), water, enzyme(s), enzyme stabilizing compound(s), dye transfer inhibitor, chelating agent(s) and pH regulator(s).
• composition of liquid detergent composition B is as follows: Component Amount [wt.-%] enzyme stabilizing compound(s) 10 - 18 alkyl sulfonates (anionic surfactant) 4 - 10 fatty alcohol sulfates (anionic surfactant) 5 - 10 sulfates of ethoxylated fatty alcohols (anionic surfactant) 4 - 10 (salts of) fatty acids (anionic surfactant) 3 - 10 ethoxylated alcohols (nonionic surfactant) 15 - 22 pH regulating compound(s) 1 - 5 chelating agent 0.1 - 0.8 lipase(s) (active content) 0.01 - 0.05 cellulase(s) (active content) 0.001 - mannanase(s) (active content) 0.001 - 0.06 pectinase(s) (active content) 0.001 - 0.05 anti-pilling cellulase(s)
• liquid detergent composition B The aspects of liquid detergent composition B are:
• the third partial composition of the detergent kit or detergent dosing system is represented by liquid detergent composition C. It is related to control the hardness of the laundry washing water and assist in soil removal.
• Said composition therefore comprises an organic builder or a mixture of organic builders and/or at least one chelating agent.
• the organic builder or the mixture of organic builders may comprise any corresponding builders described above and is, due to better solubility and for ecological benefits, preferably selected from citric acid, salts thereof and/or polymeric builders.
• Polymeric builders prevent soil-redeposition, encrustation of builders on fabrics, improve soil dispersion and assist in removal of particular stains and are preferably selected from water-soluble homopolymers comprising acrylic and/or methacrylic monomers as defined above, copolymers of two or more monomers, wherein at least one monomer is selected from the group comprising acrylic acid, methacrylic acid and/or maleic acid, mixtures thereof and/or salts thereof.
• Particularly preferred builders are citric acid and/or salts thereof.
• Liquid detergent composition C is preferably free of surfactants and/or enzymes. Due to the absence of enzymes in liquid detergent composition C, it is possible to incorporate a builder or a mixture of builders in particularly high amounts into said composition C.
• the builder or the mixture of builders may be present in liquid detergent composition C in an amount of between 10 wt.-% to 90 wt.-%, preferably from 12.5 wt.-% to 60 wt.-%, more preferred from 15 wt.-% to 50 wt.-%, most preferred from 17.5 wt.-% to 30 wt.-% of liquid detergent composition C.
• a further type of ingredient present in liquid detergent composition C is at least one complexing agent as defined above, preferably selected from MGDA, GLDA, DTPMP and/or salts thereof, wherein each complexing agent may be present in liquid detergent composition C in an amount between 0.1 wt.-% and 10 wt.-%, preferably from 0.3 wt.-% to 5 wt.-%, more preferred from 0.5 wt.-% to 2.5 wt.-% of the liquid detergent composition C.
• the total amount of complexing agent(s) present in liquid detergent composition C may be between 0.1 wt.-% and 25 wt.-%, preferably from 0.3 wt.-% to 18 wt.-%, more preferred from 0.5 wt.-% to 14 wt.-%, most preferred 0.8 wt.-% to 10 wt.-% of the liquid detergent composition C.
• Liquid detergent composition C may further comprise a polymeric builder to support the citrate in order to prevent soil-redeposition, encrustation of builders on fabrics, improve soil dispersion and assist in removal of particular stains.
• a polymeric builder preferably comprises a copolymer of acrylic acid and methacrylic acid and/or a salt, preferably a sodium salt, thereof.
• a preferred example of such a polymeric builder is Sokalan® CP5, available from BASF.
• liquid detergent composition C is at least one pH controlling agent, preferably comprising sodium hydroxide, monoethanol amine and/or triethanol amine. Said compound(s) is/are added in an amount allowing to balance the final pH in a 10% wt./vol. wash liquor to a desired value.
• pH controlling agent preferably comprising sodium hydroxide, monoethanol amine and/or triethanol amine.
• the liquid detergent composition C is essentially consisting of the above-mentioned ingredients, namely organic builder(s), organic solvent(s), chelating agent(s), water and pH regulator.
• An example of a composition of liquid detergent composition C is as follows: Component Amount [wt.-%] organic builder(s) 17.5 - 30 pH controlling compound 7 - 20 chelating agent(s) 1 - 8 performance polymer 1 - 6 water to balance
• the optional fourth and fifth partial compositions of the detergent kit or dosing system is represented by liquid detergent compositions D1 and D2.
• the bleaching agent(s) are separated from bleach activator(s) and/or bleach catalyst(s) by providing at least two partial compositions D1 and D2, i.e. the bleaching agent(s) are incorporated into composition D1, while the bleach activator(s) and/or bleach catalyst(s) are incorporated into composition D2.
• Said compositions D1 and D2 are advantageously mixed when required to produce bleach-active composition D, which is consequently added to the washing liquor.
• compositions D1 and D2 may be separately dosed into the washing liquor during any desired washing cycle.
• any bleaching agent(s), bleach activator(s) and/or bleach catalyst(s) known in the art may be used within liquid compositions D1 and D2.
• bleaching agent, bleach activator and/or bleach catalyst from ingredients like enzymes, surfactants and builders is further advantageous in order to avoid interactions between said compounds, which would otherwise decrease storage stability of the compositions.
• enzymes could be decomposed or precipitated by bleaching agents or catalysts, while bleach catalysts could be decomposed or deactivated by complexing agents or builders.
• a further advantage of storing bleach active compounds separately from the other partial compositions is the possibility to provide heavy duty or color detergents as required by the consumer.
• the optional sixths partial composition of the detergent kit or dosing system is represented by liquid detergent composition E.
• Said composition is related to provide a fabric softener composition.
• Composition E may typically comprise (cationic) surfactants, organic solvent(s), water, emulsifiers, electrolytes and pH adjusters.
• Cationic surfactants which may be present in liquid detergent composition E comprise surfactants of the quat type.
• Such surfactants are quaternary ammonium salts containing short (C 1 -C 4 ) and long (C 9 -C 20 ) alkyl, alkanol and/or ester residues.
• Preferred cationic surfactants comprise those of the ester-quat type, i.e. quaternary ammonium salts containing fatty acid esters of di- or triethanolamine.
• said composition may further comprise any ingredients suitable for a fabric softener composition known to a skilled person, such as surfactants, polysiloxanes, perfumes, perfume carriers, perfume microcapsules, fluorescent agents, dyes, soil release polymers, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, dye transfer inhibitors, antimicrobial active agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatics, bittering agents, ironing aids, phobing and impregnating agents and UV absorbers, without being limited thereto.
• surfactants such as surfactants, polysiloxanes, perfumes, perfume carriers, perfume microcapsules, fluorescent agents, dyes, soil release polymers, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, dye transfer inhibitors, antimicrobial active agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatics, bittering agents, ironing aids
• the detergent kit or detergent dosing system comprises at least three different partial liquid detergent compositions, represented by the above-mentioned liquid detergent compositions A, B and C, and optionally at least one further partial liquid detergent composition(s), represented by the liquid detergent compositions D (which is advantageously separated into compositions D1 and D2) or E, preferably compositions D and E.
• composition V1 represents a detergent composition known in the art
• E1 represents detergent composition B
• E2-E3 represent embodiments of detergent composition A according to the present invention.
• the compositions consisted of the following components (amounts given in wt.-% of the respective composition). All enzymes were received from Novozymes AS.
• liquid detergent composition according to the present invention yields improved enzyme stability after four weeks of storage at 30 °C.
• the residual content of active amylase enzyme was determined after compositions V1, E2 and E3 were stored for 4 weeks at 30 °C. Residual amylase content (% of total content of amylase enzyme) V1 E2 E3 92 92 99
• Examples 3 and 4 demonstrate that compositions according to the present invention, despite comprising a significantly higher amount of protease and alkylbenzene sulfonic acid than a typical detergent composition known in the art, show equal or even better enzyme stability.

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• 2020
  • 2020-04-06 EP EP20168122.8A patent/EP3892707A1/fr active Pending

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