EP2922943B1 - Polyamines polyalkoxylées améliorant le pouvoir détergent primaire - Google Patents

Polyamines polyalkoxylées améliorant le pouvoir détergent primaire Download PDF

Info

Publication number
EP2922943B1
EP2922943B1 EP13792931.1A EP13792931A EP2922943B1 EP 2922943 B1 EP2922943 B1 EP 2922943B1 EP 13792931 A EP13792931 A EP 13792931A EP 2922943 B1 EP2922943 B1 EP 2922943B1
Authority
EP
European Patent Office
Prior art keywords
mol
acid
weight
atoms
polyamine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13792931.1A
Other languages
German (de)
English (en)
Other versions
EP2922943A1 (fr
Inventor
Inga Kerstin Vockenroth
Nicole PLATH
Eva-Maria Wikker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP2922943A1 publication Critical patent/EP2922943A1/fr
Application granted granted Critical
Publication of EP2922943B1 publication Critical patent/EP2922943B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to the use of certain alkoxylated polyamines to enhance the primary detergency of laundry detergents or cleaners when washing textiles or cleaning hard surfaces against, in particular soiling of fruit-containing preparations, and detergents and cleaners containing such alkoxylated polyamines.
  • Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors.
  • Such excipients also include substances whose presence enhances the detergency of surfactants, without them usually having to have a surfactant behavior itself. The same applies mutatis mutandis to cleaners for hard surfaces.
  • Alkoxylated polyamines and their use in detergents and cleaners are known, for example, from international patent applications WO 95/32272 A1 and WO 2006/108857 A1 known. From the international patent application WO 2006/108856 A1
  • amphiphilic water-soluble alkoxylated polyamines having an inner polyoxyethylene block and an outer polyoxypropylene block are known.
  • ethoxylated and propoxylated polyamines have particularly good primary-detergency enhancing properties if the proportion of propoxylene groups in the entirety of the alkoxy groups does not leave a certain range. The effect is particularly pronounced if one seeks the removal of fruitous soils.
  • the invention therefore provides the use of polyalkoxylated polyamines which are obtainable by reacting polyamines with ethylene oxide and propylene oxide, wherein the proportion of propylene oxide in the total amount of the alkylene oxide 2 mol% to 18 mol%, especially 8 mol% to 15 Mol% is, in detergents or cleaners to enhance the primary washing or cleaning power when washing textiles or when cleaning hard surfaces against soiling, with fruit-containing preparations.
  • Another object of the invention is a method for removing stains of fruit-containing preparations of textiles or hard surfaces, in which a detergent or cleaning agent and a said polyalkoxylated polyamine are used.
  • This method can be carried out manually or mechanically, for example by means of a household washing machine or dishwasher. It is possible to apply the particular liquid agent and the active ingredient simultaneously or sequentially. The simultaneous application can be carried out particularly advantageously by the use of an agent which contains the active ingredient.
  • the concentration of said polyalkoxylated polyamine in the particular aqueous washing or cleaning liquor is preferably 1 mg / l to 500 mg / l, in particular 5 mg / l to 200 mg / l.
  • the polyalkoxylated polyamine is a polymer having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms.
  • the polyamine has primary amino functions at the ends and preferably both secondary and tertiary amino functions inside; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine.
  • the ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1.
  • the ratio of primary to tertiary amino groups in the polyamine is preferably in the range from 1: 0.2 to 1: 1, in particular in the range from 1: 0.5 to 1: 0.8.
  • the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol.
  • the mean molar masses indicated here and later, if appropriate, for other polymeric ingredients are weight-average molar masses M w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard.
  • the N atoms in the polyamine are preferably separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof.
  • the primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function must be alkoxy group substituted.
  • the average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 100, in particular 5 to 70.
  • the alkoxy groups in the polyalkoxylated polyamine are propoxy and ethoxy groups which are bonded directly to N atoms, and optionally to propoxy and ethoxy groups which are bonded to propoxy or ethoxy radicals.
  • the polyalkoxylated polyamines are obtainable by reacting polyamines with propylene oxide and ethylene oxide, wherein propylene oxide and ethylene oxide together or first of all propylene oxide and then ethylene oxide or first ethylene oxide and then propylene oxide can be used.
  • the average number of alkoxy groups per primary and secondary amino function in the polyalkoxyated polyamine is preferably from 1 to 100, in particular from 5 to 70.
  • the terminal OH function of at least some of the polyalkoxy substituents may be replaced by an alkyl ether function having from 1 to 10, in particular 1 to 3, carbon atoms .
  • Fruit-containing preparations are nutritionally suitable fruit preparations, such as jams, jams and jellies. These lead due to their thickener content and their fruit content to difficult to remove stains.
  • the use according to the invention of the palyalkaxylated polyamine is preferably carried out in detergents or cleaners by mixing it in an amount of 0.1% by weight to 10% by weight, in particular in an amount of 0.2% by weight to 2 % By weight, in which case the statements of "% by weight" here and in the following apply in each case to the weight of the entire washing or cleaning agent, unless stated otherwise.
  • Detergents or cleaning agents containing polyalkoxylated polyamine obtainable by reacting polyamines with ethylene oxide and propylene oxide, wherein the proportion of propylene oxide in the total amount of the alkylene oxide 2 mol% to 18 mol%, in particular 8 mol% to 15 mol% % is.
  • Detergents or cleaning agents which contain or are used together with an active substance to be used according to the invention or are used in the process according to the invention may contain all customary other constituents of such agents which do not interact in an undesired manner with the active ingredient essential to the invention.
  • the washing or cleaning agent preferably contains an active substance as defined above in amounts of at least 0.1% by weight, in particular from 0.2% by weight to 2% by weight.
  • An agent which contains or is used together with an active substance to be used according to the invention or is used in the process according to the invention preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular of 0.1 wt .-% to 18 wt .-%, each based on the total agent.
  • Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which contain an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as a counter cation to call.
  • the alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • the sulfate-type surfactants which can be used with particular preference include the abovementioned sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
  • Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.
  • the anionic surfactants which can be used also include the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • Another synthetic anionic surfactant is alkylbenzenesulfonate in question.
  • compositions comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and the like Mixtures, in particular in an amount in the range of 2% by weight to 25% by weight.
  • nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and the like Mixtures,
  • Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
  • the alkoxylates in particular the ethoxylates, of primary alcohols with linear, in particular, are useful Dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
  • suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
  • the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and Fettklarepolyhydroxyamide into consideration.
  • alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) n -OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
  • the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomermaschinesgrad.
  • the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
  • Preferred monomer building block is glucose because of its good availability.
  • Nonionic surfactant is present in compositions which contain an active ingredient used according to the invention or are used in the context of the use according to the invention, preferably in amounts of from 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight. With amounts in the upper part of this range being more likely to be found in liquid detergents and particulate detergents preferably containing lower amounts of up to 5% by weight.
  • soaps suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • soap is included in amounts of from 0.1% to 5% by weight.
  • higher amounts of soap can be contained, usually up to 20 wt .-%.
  • compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.
  • betaines and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.
  • esterquats are particularly preferred.
  • the compositions may contain peroxygen bleaching agents, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activators, especially in amounts ranging from 2% to 10% by weight.
  • the bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts.
  • Such bleaching agents are in detergents containing an active ingredient according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on total agent, present, in particular percarbonate is used.
  • the optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and also cationic nitrile derivatives such as trimethylammonium acetonitrile salts.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetyl
  • the bleach activators may have been coated and / or granulated in a known manner with coating substances, granulated tetraacetylethylenediamine having mean particle sizes of 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or in particulate form, trialkylammonium acetonitrile is particularly preferred.
  • Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
  • the composition contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
  • water-soluble and / or water-insoluble builder in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
  • the agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • the water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular the Polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid ,
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to 100,000 g / mol.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • the acid content is at least 50% by weight.
  • Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt. % of a carbohydrate.
  • This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
  • These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol.
  • polycarboxylic acids can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions.
  • All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar ratio of Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 are preferably added in the course of the production as a solid and not in the form of a solution.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + 1 ⁇ are used yH 2 O, in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • amorphous alkali metal silicates practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1.9 to 2.1, can be used in agents which contain an active ingredient to be used according to the invention.
  • a crystalline sodium layer silicate is used with a modulus of 2 to 3, as it can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention.
  • alkali metal silicates are preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • water-soluble or water-insoluble inorganic substances may be contained in the agents containing an active ingredient to be used according to the present invention, used together with it or used in methods of the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.
  • the agents may contain other ingredients customary in detergents or cleaners.
  • these optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
  • agents which contain an active substance used according to the invention up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-tri-amino-s-triazinyl) -stilbene-2,2'-disulphonic acids, up to 5% by weight, in particular from 0.1% by weight to 2% by weight
  • optical brighteners in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-tri-amino-s-triazinyl) -stilbene-2,2'-disulphonic acids
  • up to 5% by weight in particular from 0.1% by weight to 2% by weight
  • Complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts and up to 2% by weight, in particular from 0.1% by weight to 1% by weight, of foam inhibitors, the weight proportions in each case referring to the total agent.
  • Solvents that can be used in particular for liquid agents are, in addition to water, preferably those nonaqueous solvents which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, iso-propanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and those mentioned Classes of derivable ether.
  • the active compounds used in the invention are usually dissolved or in suspended form.
  • Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof.
  • proteases derived from microorganisms such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms.
  • Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
  • the lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species.
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase.
  • Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm.
  • the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
  • Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
  • Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
  • enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.
  • Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances.
  • polyester-active soil release polymers which can be used in addition to the essential ingredients of the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or Polypropylene glycol.
  • dicarboxylic acids for example adipic acid, phthalic acid or terephthalic acid
  • diols for example ethylene glycol or propylene glycol
  • polydiols for example polyethylene glycol or Polypropylene glycol.
  • Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 denotes hydrogen
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range of 4 to 200, particularly 12 to 140.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyester is in the range of 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol.
  • the acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
  • acids having at least two carboxyl groups may be included in the soil release-capable polyester.
  • these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • the preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • R 11 is hydrogen and a is a number from 2 to 6
  • R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol.
  • the polyesters may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
  • the ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
  • valeric acid caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, Myristoleic, pentadecanoic, palmitic, stearic, petroselinic, petroselaidic, oleic, linoleic, linolaidic, linolenic, levostic, arachidic, gadoleic, arachidonic, behenic, erucic, brassidic, clupanodonic, lignoceric, cerotic a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example, tert-butylbenzoic acid.
  • the end groups may also be based on hydroxymonocarboxylic acids having from 5 to 22 carbon atoms, including, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which include hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid.
  • the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
  • polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10 used in combination with an essential ingredient of the invention.
  • the soil release polymers are preferably water-soluble, the term "water-soluble" being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8.
  • preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.
  • compositions according to the invention having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
  • compositions in tablet form which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
  • the procedure is preferably such that all components - optionally one layer at a time - in a mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric presses or rotary presses, with pressing forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN.
  • a tablet produced in this way has a weight of from 10 g to 50 g, in particular from 15 g to 40 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
  • Liquid or pasty compositions in the form of common solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • an agent which is incorporated into the active ingredient to be used according to the invention is liquid and contains 1% by weight to 15% by weight, in particular 2% by weight to 10% by weight, of nonionic surfactant, 2% by weight.
  • % to 30% by weight in particular 5% by weight to 20% by weight of synthetic anionic surfactant, up to 15% by weight, in particular 2% by weight to 12.5% by weight of soap, 0, 5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, in particular polycarboxylate such as citrate, up to 1.5 wt .-%, in particular 0.1 wt .-% to 1 wt .-% complexing agent for heavy metals, such as phosphonate, and in addition to optionally contained enzyme, enzyme stabilizer, color and / or perfume, water and / or water-miscible solvent.
  • an agent in which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular from 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15% by weight .-%, in particular 1 wt .-% to 10 wt .-% bleach activator, 20 wt .-% to 55 wt .-% inorganic builder, up to 10 wt .-%, in particular 2 wt .-% to 8 wt.
  • bleaching agent in particular alkali percarbonate
  • alkali percarbonate up to 15% by weight .-%, in particular 1 wt .-% to 10 wt .-% bleach activator, 20 wt .-% to 55 wt .-% inorganic builder, up to 10 wt .-%, in particular 2 wt .-% to 8 wt.
  • % water-soluble organic builder 10% to 25% by weight synthetic anionic surfactant, 1% to 5% by weight nonionic surfactant and up to 25% by weight, in particular 0.1% by weight to 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.
  • Table 1 Detergent compositions (in% by weight) A B C D e F G H C9-13-Alkylbenzenesulfonate, Na salt 9 10 6 6 5 15 15 9 C12-18 fatty alcohol with 7 EO 8th 9 6 6 5 6 6 10 C12-14 fatty alcohol sulfate with 2EO - - 8th 8th 10 2 2 5 C12-18 fatty acid, Na salt 4 3 3 - 4 - 2 - 7 citric acid 2 3 3 3 2 2 2 3 sodium hydroxide 3 3 2 2 3 3 3 4 boric acid 1 1 1 1 1 1 1 1 1 enzymes + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +
  • Household washing machines (Miele® W 1514) were loaded with 3.5 kg of clean accompanying laundry and with test cloths of cotton and dirt ballast provided with the standardized soiling (A: blackcurrant jelly: B: sour cherry jam) given in table 2.
  • the detergents with an active ingredient to be used according to the invention showed a significantly better primary washing performance than the otherwise identically composed compositions with a polyethyleneimine not to be used according to the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (8)

  1. Utilisation de polyamines polymères polyalcoxylés qui peuvent être obtenus par conversion de polyamines polymères avec de l'oxyde d'éthylène et de l'oxyde de propylène, la teneur en oxyde de propylène rapportée à la quantité totale d'oxyde d'alkylène étant de 2 % en moles à 18 % en moles, dans des produits de lavage ou de nettoyage pour renforcer le pouvoir lavant ou nettoyant primaire au cours du lavage de textiles ou de nettoyage de surfaces dures contre les salissures comportant des préparations contenant des fruits.
  2. Procédé d'élimination de salissures, comportant des préparations contenant des fruits, de textiles ou de surfaces dures, dans lequel on utilise un produit lavant ou nettoyant et une polyamine polymère polyalcoxylée qui peut être obtenue par conversion de polyamines polymères avec de l'oxyde d'éthylène et de l'oxyde de propylène, la teneur en oxyde de propylène rapportée à la quantité totale d'oxyde d'alkylène étant de 2 % en moles à 18 % en moles.
  3. Procédé selon la revendication 2, caractérisé en ce que la concentration de la polyamine polyalcoxylée dans le bains de lavage ou de nettoyage en particulier aqueux est de 1 mg/l à 500 mg/l, en particulier de 5 mg/l à 200 mg/l.
  4. Utilisation selon la revendication 1 ou procédé selon la revendication 2 ou 3, caractérisé en ce que les atomes d'azote dans la polyamine sont séparés les uns des autres par des groupes alkyles comportant 2 à 12 atomes de carbone, en particulier 2 à 6 atomes de carbone, aucuns des groupes alkyles ne devant avoir le même nombre d'atomes de carbone.
  5. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé en ce que la polyamine a une masse molaire moyenne dans la gamme de 500 g/mol à 50000 g/mol, en particulier de 550 g/mol à 5000 g/mol.
  6. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé en ce que le nombre moyen de groupes alcoxy par fonction amine primaire et secondaire dans la polyamine polyalcoxylée est de 1 à 100, en particulier de 5 à 70.
  7. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé en ce que la teneur en oxyde de propylène rapportée à la quantité totale d'oxyde d'alkylène est de 8 % en moles à 15 % en moles.
  8. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé en ce que, dans l'amine polyalcoxylée, la fonction -OH terminale d'au moins certains des substituants polyalcoxy est remplacée par une fonction alkyléther comportant 1 à 10, en particulier 1 à 3, atomes de carbone.
EP13792931.1A 2012-11-26 2013-11-21 Polyamines polyalkoxylées améliorant le pouvoir détergent primaire Active EP2922943B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012221573.5A DE102012221573A1 (de) 2012-11-26 2012-11-26 Die Primärwaschkraft verbessernde polyalkoxylierte Polyamine
PCT/EP2013/074327 WO2014079905A1 (fr) 2012-11-26 2013-11-21 Polyamines polyalkoxylées améliorant le pouvoir détergent primaire

Publications (2)

Publication Number Publication Date
EP2922943A1 EP2922943A1 (fr) 2015-09-30
EP2922943B1 true EP2922943B1 (fr) 2018-04-11

Family

ID=49622837

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13792931.1A Active EP2922943B1 (fr) 2012-11-26 2013-11-21 Polyamines polyalkoxylées améliorant le pouvoir détergent primaire

Country Status (4)

Country Link
US (1) US20150252293A1 (fr)
EP (1) EP2922943B1 (fr)
DE (1) DE102012221573A1 (fr)
WO (1) WO2014079905A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017131691A1 (fr) 2016-01-28 2017-08-03 Kimberly-Clark Worldwide, Inc. Composition anti-adhérente contre les virus à adn et procédé d'inhibition de l'adhérence des virus à adn à une surface
MX2018008221A (es) * 2016-01-28 2018-09-07 Kimberly Clark Co Composicion adherente para virus de acido ribonucleico (arn) y metodo para eliminar virus de acido ribonucleico (arn) de una superficie.

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
PE6995A1 (es) 1994-05-25 1995-03-20 Procter & Gamble Composicion que comprende un polimero de polialquilenoamina etoxilado propoxilado como agente de separacion de sucio
US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
US6156720A (en) * 1998-06-23 2000-12-05 Basf Aktiengesellschaft Propoxylated/ethoxylated polyalkyleneimine dispersants
US8669221B2 (en) 2005-04-15 2014-03-11 The Procter & Gamble Company Cleaning compositions with alkoxylated polyalkylenimines
US7820610B2 (en) * 2008-04-07 2010-10-26 The Procter & Gamble Company Laundry detergent containing polyethyleneimine suds collapser
CN102037112A (zh) * 2008-05-28 2011-04-27 宝洁公司 具有良好稳定性的织物软化衣物洗涤剂
EP2478083B1 (fr) * 2009-09-14 2018-01-03 The Procter and Gamble Company Systeme de structuration externe pour composition liquide de detergent a lessive
ES2646416T3 (es) * 2012-05-11 2017-12-13 The Procter & Gamble Company Composición detergente

Also Published As

Publication number Publication date
WO2014079905A1 (fr) 2014-05-30
DE102012221573A1 (de) 2014-05-28
EP2922943A1 (fr) 2015-09-30
US20150252293A1 (en) 2015-09-10

Similar Documents

Publication Publication Date Title
DE102017010656A1 (de) Wasch- und Reinigungsmittel mit polymerem Wirkstoff
DE102017010654A1 (de) Wasch- und Reinigungsmittel mit polymerem Wirkstoff
DE102011089948A1 (de) Die Primärwaschkraft verbessernde polyalkoxylierte Polyamine
WO2013152992A1 (fr) Cellulose microfibrillaire en tant que substance active à pouvoir détachant
EP3280788B1 (fr) Détergents et produits de nettoyage à principe actif polymère
EP2753683A1 (fr) Principes actifs polymères améliorant le pouvoir détergent primaire
EP2753650A1 (fr) Principes actifs polymères améliorant le pouvoir détergent primaire
EP2931858B1 (fr) Produits détergents et nettoyants contenant une polyamine polyalcoxylée et un tensioactif non ionique adapté
WO2016162253A1 (fr) Détergents et produits de nettoyage à principe actif polymère
EP2931769B1 (fr) Principes actifs polymères améliorant le pouvoir détergent primaire
EP2922943B1 (fr) Polyamines polyalkoxylées améliorant le pouvoir détergent primaire
EP3227421B1 (fr) Détergents et produits de nettoyage à principe actif polymère
DE102017128126A1 (de) Wasch- und Reinigungsmittel mit optischem Aufheller
EP3227423B1 (fr) Compositions détergentes comprenant un agent actif polymère
EP2922634A1 (fr) Principes actifs polymères contenant des groupes sulfonates améliorant le pouvoir détergeant
EP2931863B1 (fr) Principes actifs polymères améliorant le pouvoir détergent primaire
DE102015212963A1 (de) Die Primärwaschkraft verbessernde polymere Wirkstoffe
DE102022200126A1 (de) Fucoidane als vergrauungsinhibierende Wirkstoffe
DE102022200882A1 (de) Polymere schmutzablösevermögende Wirkstoffe
DE102012220103A1 (de) Die Primärwaschkraft verbessernde Tensidkombination
DE19934983A1 (de) Verwendung von Polyvinylalkoholen als schmutzablösevermögende Waschmittelzusätze

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150518

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20171020

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

GRAR Information related to intention to grant a patent recorded

Free format text: ORIGINAL CODE: EPIDOSNIGR71

INTC Intention to grant announced (deleted)
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

INTG Intention to grant announced

Effective date: 20180302

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 988031

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180415

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502013009909

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180411

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180711

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180711

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180712

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180813

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502013009909

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

26N No opposition filed

Effective date: 20190114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181121

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20181130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181130

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181130

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 988031

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20181121

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180411

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20131121

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180411

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20180811

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231123

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231120

Year of fee payment: 11

Ref country code: DE

Payment date: 20231121

Year of fee payment: 11