EP3049508B1 - Carbamates de cellulose utilisés comme principes actifs ayant la capacité de dissoudre les saletés - Google Patents

Carbamates de cellulose utilisés comme principes actifs ayant la capacité de dissoudre les saletés Download PDF

Info

Publication number
EP3049508B1
EP3049508B1 EP14776608.3A EP14776608A EP3049508B1 EP 3049508 B1 EP3049508 B1 EP 3049508B1 EP 14776608 A EP14776608 A EP 14776608A EP 3049508 B1 EP3049508 B1 EP 3049508B1
Authority
EP
European Patent Office
Prior art keywords
groups
acid
weight
cellulose
cellulose carbamate
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.)
Not-in-force
Application number
EP14776608.3A
Other languages
German (de)
English (en)
Other versions
EP3049508A1 (fr
Inventor
Mareile Job
Frank Janssen
Christian Kropf
Christa JUNKES
Michael STROTZ
Thomas Heinze
Kristin Ganske
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 EP3049508A1 publication Critical patent/EP3049508A1/fr
Application granted granted Critical
Publication of EP3049508B1 publication Critical patent/EP3049508B1/fr
Not-in-force 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

  • the present invention relates to the use of certain soil release agents to enhance the cleaning performance of laundry detergents in laundry.
  • 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 adjuvants also include substances which impart soil repellency properties to the laundry fiber and, if present during the wash, aid the soil release properties of the remaining detergent ingredients. The same applies mutatis mutandis to cleaners for hard surfaces.
  • soil release agents are often referred to as “soil release” agents or because of their ability to render the treated surface, e.g., the fiber, soil-repellent as "soil repellents”.
  • the US patent US 4,000,093 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight surfactant, wherein the surfactant component is substantially consists of C 10 - to C 13 -alkyl sulfate and up to 5 wt .-% C 14 alkyl sulfate and less than 5 wt .-% alkyl sulfate having alkyl radicals of C 15 and higher.
  • copolyesters containing dicarboxylic acid units such as terephthalic acid or sulfoisophthalic acid, alkylene glycol units such as ethylene glycol or propylene glycol and polyalkylene glycol units such as polyethylene glycol.
  • dicarboxylic acid units such as terephthalic acid or sulfoisophthalic acid
  • alkylene glycol units such as ethylene glycol or propylene glycol
  • polyalkylene glycol units such as polyethylene glycol.
  • the polymers known from the prior art have the disadvantage that, in particular for textiles which are not or at least not predominantly made of polyester, have no or only insufficient effectiveness.
  • a large part of today's textiles consists of cotton or cotton-polyester blend fabrics, so that there is a need for especially greasy soiling on especially such textiles more effective soil release agents.
  • the cellulose carbamate to be used according to the invention contains further 1,4-.beta.-glycosidically linked anhydroglucose units, which may be unsubstituted or likewise correspond to the general formula I.
  • anhydroglucose residues with other substituents, for example alkyl groups such as methyl or ethyl groups, hydroxyalkyl groups such as hydroxyethyl or hydroxypropyl groups or oligoethoxyethyl or oligopropoxypropyl groups, carboxyalkyl groups such as carboxymethyl or carboxyethyl groups, aminoalkyl groups such as aminoethyl or trimethylammoniumethyl groups, sulfoalkyl groups such as sulfoethyl or Sulfopropyl groups, ester groups such as acetic, .beta.-aminopropionic, glycolic or malonic acid ester groups.
  • substituents for example alkyl groups such as methyl or ethyl groups, hydroxyalkyl groups such as hydroxyethyl or hydroxypropyl groups or oligoethoxyethyl or oligopropoxypropyl groups, carboxyalkyl groups such as
  • the average degree of substitution, based on the proportion of carbamate groups, in the cellulose carbamate to be used according to the invention is preferably in the range from 0.2 to 2, in particular from 0.4 to 1.2. If other substituents are present in addition to carbamate groups, the average degree of substitution, based on the proportion of such other groups, is preferably below 1 and in particular below the degree of substitution for the carbamate groups.
  • Another object of the invention is a process for washing textiles, in which a detergent and a soil release agent in the form of a cellulose carbamate as defined above are used. These methods can be carried out manually or optionally with the aid of a conventional household washing machine. It is possible to use the detergent and soil release agent simultaneously or sequentially. The simultaneous application can be particularly advantageous by the use of a detergent containing the soil release agent, perform.
  • the effect of the active ingredient to be used according to the invention in the case of multiple use, that is to say, in particular for the removal of stains from textiles, which had already been washed and / or post-treated in the presence of the active substance before being soiled.
  • the designated positive aspect can also be realized by a washing process in which the textile after the actual washing process, with the help of a detergent which may contain a named active ingredient, but in this case also free may be carried out by this, with an aftertreatment agent, for example in the context of a fabric softening step, which contains an active substance to be used according to the invention is brought into contact.
  • the active ingredient used according to the invention leads to a significantly better detachment of, in particular, grease and cosmetic soilings on textiles, in particular those made of cotton or cotton-containing fabric, than is the case when compounds previously known for this purpose are used. Alternatively, significant amounts of surfactants can be saved while maintaining fat removal capability.
  • the use according to the invention can be carried out as part of a washing process by adding the soil release agent to a detergent-containing liquor or preferably incorporating the active ingredient as a component of a detergent into the liquor containing or to be contacted with the object to be cleaned.
  • Further objects of the invention are therefore detergents which contain above-defined cellulose carbamates.
  • laundry aftertreatment process can be carried out in such a manner that the rinse liquor is added separately to the rinse liquor which is used after the wash cycle using a particular bleach-containing detergent, or it is incorporated as a component of the laundry aftertreatment agent, in particular a softener.
  • the laundry detergent used before the laundry aftertreatment agent may also contain, but may be free from, an active ingredient to be used according to the invention.
  • the washing process is preferably carried out at a temperature of 15 ° C to 60 ° C, more preferably at a temperature of 20 ° C to 40 ° C.
  • the washing process is furthermore preferably carried out at a pH of 6 to 11, particularly preferably at a pH of 7.5 to 9.5.
  • the use concentration of the cellulose carbamate in the wash liquor is preferably from 0.001 g / l to 1 g / l, in particular from 0.005 g / l to 0.2 g / l.
  • Agents which contain an active ingredient to be used according to the invention in the form of said cellulose carbamate or are used together or used in the method according to the invention may contain all customary other constituents of such agents which do not undesirably interact with the active substance essential to the invention, in particular surfactant.
  • the active substance defined above is preferably used in amounts of from 0.01% by weight to 10% by weight, particularly preferably from 0.1% by weight to 3% by weight, these and the following quantities being based on refer to the total amount, unless stated otherwise.
  • the active ingredient used according to the invention has a positive effect on the action of certain other detergent ingredients and conversely that the effect of the soil release active ingredient is additionally enhanced by certain other detergent ingredients.
  • these effects occur in particular with bleaching agents, with enzymatic active substances, in particular proteases and lipases, with water-soluble inorganic and / or organic builders, in particular based on oxidized carbohydrates or polymeric polycarboxylates, with synthetic anionic surfactants of the sulphate and sulphonate type, and with color transfer inhibitors, for example vinylpyrrolidone , Vinylpyridin- or vinylimidazole polymers or copolymers or corresponding Polybetainen on, which is why the use of at least one of said further ingredients together with the invention to be used drug is preferred.
  • An agent which contains an active substance to be used according to the invention or is used together or is used in the process according to the invention preferably contains peroxygen-based bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally However, bleach activator, especially in amounts ranging from 2% to 10% by weight, may in another preferred embodiment also be free of bleach and bleach activator.
  • 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 in the form of tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts.
  • percarboxylic acids for example dodecanedioic acid or phthaloylaminoperoxicaproic acid
  • hydrogen peroxide alkali metal perborate
  • percarbonate 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 optional component of the bleach activators includes 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, sulfururamides and cyanurates, moreover carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulphonate, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammonium acetonitrile salts.
  • N- or O-acyl compounds for example, polyacylated alkylenediamines, in particular tetraacetylethylenediamine
  • the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having weight-average particle sizes of from 0.01 mm to 0.8 mm, granulated 1.5% by means of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or formulated in particulate 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.
  • an agent used according to the invention or used in the process according to the invention comprises nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, especially 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 mixtures thereof, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
  • Such agents comprises the presence of sulfate and / or sulfonate synthetic anionic surfactant, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid ester and / or sulfo fatty acid salt, in particular in an amount in the range from 2% to 25% by weight.
  • the anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms. These are usually not individual substances, but cuts or mixtures. Of these, preference is given to those whose content of compounds having longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.
  • 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, primary alcohols with linear, especially 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 used in compositions containing a soil release agent used in the invention, used according to the invention or used in the process according to the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 Wt .-%, with amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain rather lower amounts of up to 5 wt .-%.
  • the agents may instead or additionally contain other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight. %, in each case based on total resources.
  • 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 Wear countercation, to name.
  • 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.
  • Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as 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.
  • 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 as a rule up to 20% by weight, can also be present.
  • 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 discussed below are particularly preferred.
  • 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, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, Maleic acids and copolymers of these, 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, that 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 can 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 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid 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 can 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 or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid 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 3000 g / mol and 10000 g / mol. They 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 used 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 mm and preferably consist of at least 80% by weight of particles having a size of less than 10 mm.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali 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®. They 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.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both .beta.- and ⁇ -Natriumdisitikate (Na 2 Si 2 O 5 ⁇ yH 2 O) are preferred.
  • amorphous alkali metal silicates can be used in agents which contain an active ingredient to be used according to the invention.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as prepared from sand and soda can be.
  • 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 compositions which contain an active substance to be used according to the invention together with it or used in the process according to 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 and 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-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular Aminoalkylenphosphonklaren and their salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.
  • optical brighteners in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5
  • Solvents which can be used in particular for liquid agents are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether.
  • the active compounds used in the invention are usually dissolved or in suspended form.
  • enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or 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®.
  • customary enzyme stabilizers present include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid or alkali 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.
  • an agent to 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 from 1% by weight to 10% by weight of bleach activator, from 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular from 2% by weight to 8% by weight % water-soluble organic builder, 10 wt.% to 25 wt.% of synthetic anionic surfactant, 1 wt.% to 5 wt.% of nonionic surfactant and up to 25 wt.%, in particular 0.1 wt 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.
  • an agent in which the active ingredient to be used according to the invention is incorporated is liquid and contains from 1% by weight to 25% by weight, in particular from 5% by weight to 15% by weight, of nonionic surfactant, up to 10 wt .-%, in particular 0.5 wt .-% to 8 wt .-% of synthetic anionic surfactant, 3 wt .-% to 15 wt .-%, in particular 5 wt .-% to 10 wt .-% soap, 0 , 5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, especially 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
  • polyester-active soil release polymers which can be used in addition to the active compounds 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 from 4 to 200, in particular from 12 to 140.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polymers is in the range from 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.
  • their acid groups are part of the ester linkages in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt.
  • 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.
  • these polyesters composed as described above may also be end-capped, alkyl groups having 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 acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butyl
  • 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.
  • polyester-active 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.
  • Preferred laundry aftertreatment compositions which comprise an active substance to be used according to the invention have, as a laundry softening active ingredient, a so-called esterquat, that is to say a quaternized ester of carboxylic acid and aminoalcohol.
  • esterquat that is to say a quaternized ester of carboxylic acid and aminoalcohol.
  • These are known substances which can be obtained by the relevant methods of preparative organic chemistry, for example by partially esterifying triethanolamine in the presence of hypophosphorous acid with fatty acids, passing air through and then quaternizing with dimethyl sulfate or ethylene oxide.
  • the production of solid ester quats is also known, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.
  • Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow formula (IV), in the R 1 CO for an acyl radical having 6 to 22 carbon atoms, R 2 and R 3 are independently hydrogen or R 1 CO, R 4 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H Group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 and R 3 are independently hydrogen or R 1 CO
  • R 4 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H Group
  • m, n and p in total are 0 or numbers from 1 to 12
  • q is numbers from 1 to 12
  • esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils.
  • technical C 12/18 coconut fatty acids and, in particular, partially hydrogenated C 16/18 tallow or palm oil fatty acids and also elaidic acid-rich C 16/18 fatty acid cuts are used.
  • the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1.
  • an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats used are technical mixtures of mono-, di- and triesters having an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 tallow or palm oil fatty acid (iodine number 0 to 40) , Quaternized fatty acid triethanolamine ester salts of the formula (IV) in which R 1 is CO for an acyl radical having 16 to 18 carbon atoms, R 2 is R 1 CO, R 3 is hydrogen, R 4 is a methyl group, m, n and p is 0 and X is Methyl sulfate is, have proven to be particularly advantageous.
  • suitable esterquats are quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (V), in the R 1 CO for an acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen or R 1 CO, R 4 and R 5 are independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen or R 1 CO
  • R 4 , R 6 and R 7 are independently alkyl radicals having 1 to 4 carbon atoms
  • X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • ester quats are in the form of 50 to 90 percent by weight alcoholic Commercially available solutions which can also be easily diluted with water, ethanol, propanol and isopropanol being the usual alcoholic solvents.
  • Esterquats are preferably used in amounts of from 5% by weight to 25% by weight, in particular from 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent.
  • the laundry aftertreatment agents used in the present invention may additionally contain detergent ingredients listed above, unless they unduly interact negatively with the esterquat. It is preferably a liquid, water-containing agent.
  • N-.omega.-hydroxyethyl cellulose carbamate was prepared analogously to the process described under a) from cellulose phenyl carbonate and 2-aminoethanol. Yield: 28 g (99%)
  • FT-IR KBr
  • 3399 cm -1 v (OH) 2945 cm -1 -2885 cm -1 v (CH 2 ) 1710 cm -1 v (C O) 13
  • Table 1 shows the composition (ingredients in percent by weight, in each case based on the total agent) of the inventive detergents M1 to M6 and of the active ingredient free agent V1: Table 1: Compositions V1 M1 M2 M3 M4 M5 M6 C 9-13 Alkylbenzenesulfonate, Na salt 5 5 5 5 5 5 5 5 Sodium lauryl ether sulfate with 2 EO 6 6 6 6 6 6 6 C 12-14 fatty alcohol with 7 EO 5 5 5 5 5 5 C 12-18 fatty acid, Na salt 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 NaOH 2 2 2 2 2 2 2 citric acid 2 2 2 2 2 2 2 2 2 phosphonate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Active ingredient I a) - 1 - - 1.5 - - Active ingredient II b) - - 1 - - 1.5 - Active substance III c) - - - 1 - - 1.5 water on 100 a
  • Means V1, M1, M2 or M3 were tested in a Miele® W 1714 washing machine (cotton washing program, 40 ° C., water hardness 16 ° dH, standardized soil carrier, dosage 70 g of the respective product per wash cycle). In addition to filling laundry to a load of 3.5 kg, the cotton materials listed in Table 2 were used (each 8 textile pieces in the size 20 x 40 cm).
  • Table 2 shows the difference in the brightness change (delta delta Y value) of the materials after 3 washes with the respective agent M1, M2 or M3 in comparison with 3 washes with the agent V1.
  • Table 2 Brightness change to V1 Textile / Medium M1 M2 M3 WFK 10A 1.6 0.8 1.3 WFK 12A toweling 3.5 2.5 2.3 Terry towel 2.4 1.9 1.1 Krefeld standard 1.5 1.4 nb Doppelripp 3.4 1.6 1.8 EMPA 221 2.8 1.7 nb nb: not determined
  • Polyester clean textiles were washed 3 times in a Miele® W 1514 washing machine at 40 ° C. with water of 16 ° dH with the detergent V1 stated in Example 2 or with the detergents M4, M5 or M6 likewise indicated there, and then air-dried.
  • the thus prepared fabrics were again washed with the detergent V under the above conditions at a capacity of 3.5 kg (clean linen plus polyester test fabrics).
  • the evaluation was carried out colorimetrically; Table 3 shows the mean values of the brightness values (Y values) from 6-fold determinations.

Landscapes

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

Claims (10)

  1. Utilisation de carbamates de cellulose qui contiennent une unité d'anhydroglucose selon la formule générale I,
    Figure imgb0009
    dans laquelle R représente du H ou du -C(=O)-NR1R2, à la condition qu'au moins 1 des résidus R soit identique à -C(=O)-NR1R2, et
    R1 représente du H ou R2 et R2 représente un groupe aryle, un groupe alkyle, aryle, alkylaryle ou arylalkyle à chaine droite ou ramifié, qui peut être substitué par un ou plusieurs groupes fonctionnels, tels que des groupes hydroxy, carboxy, oxy ou amino, et/ou qui peut être interrompu avec des hétéroatomes, tels que N, O ou S,
    pour renforcer l'effet nettoyant d'agents de lavage lors du lavage de matières textiles.
  2. Procédé de lavage de matières textiles lors duquel l'on utilise un agent de lavage et un carbamate de cellulose, qui contient une unité d'anhydroglucose substitué selon la formule générale I,
    Figure imgb0010
    dans laquelle R représente du H ou du -C(=O)-NR1R2, à la condition qu'au moins 1 des résidus R soit identique à -C(=O)-NR1R2, et
    R1 représente du H ou R2 et R2 représente un groupe aryle, un groupe alkyle, aryle, alkylaryle ou arylalkyle à chaine droite ou ramifié, qui peut être substitué par un ou plusieurs groupes fonctionnels, tels que des groupes hydroxy, carboxy, oxy ou amino, et/ou qui peut être interrompu avec des hétéroatomes, tels que N, O ou S.
  3. Procédé selon la revendication 2, caractérisé en ce que la concentration d'emploi du carbamate de cellulose dans la matière tinctoriale de lavage s'élève de 0,001 g/l à 1 g/l, en particulier de 0,005 g/l à 0,2 g/l.
  4. Procédé selon la revendication 2 ou 3, caractérisé en ce que l'on l'exécute en utilisant un agent de lavage contenant le carbamate de cellulose.
  5. Procédé de lavage de matières textiles selon l'une des revendications 2 à 4, caractérisé en ce que l'on l'exécute en utilisant un agent de post-traitement de lavage, en particulier un agent adoucissant, contenant le carbamate de cellulose.
  6. Procédé selon l'une des revendications 2 à 5, caractérisé en ce que l'agent contient du carbamate de cellulose dans des quantités allant de 0,01 % en poids à 10% en poids, en particulier de 0,1 % en poids à 3 % en poids.
  7. Utilisation selon la revendication 1 ou procédé selon l'une des revendications 2 à 6, caractérisée en ce que, dans la formule générale I, les groupes -NR1R2 dérivent d'aminoalcools, d'amines alkoxylés à plusieurs reprises, d'acides α-aminés, d'acides β-aminés, d'acides w-aminés, d'aniline, qui peut le cas échéant être substituée sur le cycle, de benzylamine, qui peut le cas échéant être substituée sur le cycle, de morpholine, de n-amino-morpholine, de n-aminoalkylmorpholine, d'éthylènediamine, et des mélanges de ceux-ci.
  8. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé(e) en ce que le carbamate de cellulose contient, outre l'unité d'anhydroglucose substituée selon la formule générale I, d'autres unités d'anhydroglucose combinées avec celui-ci 1,4-β-glycosidiquement, qui peuvent être non-substituées ou correspondre à la formule générale I.
  9. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé(e) en ce que, dans le carbamate de cellulose, l'on trouve également des résidus d'anhydroglucose avec d'autres substituants, parmi lesquels par exemple des groupes alkyle tels que des groupes méthyl ou éthyl, des groupes hydroxyalkyles tels que des groupes hydroxyéthyl ou hydroxypropyl, des groupes carboxyalkyles tels que des groupes carboxyméthyl ou carboxyéthyl, des groupes aminoalkyles tels que des groupes aminoéthyl ou triméthylammoniuméthyl, des groupes sulfoalkyles tels que des groupes sulfoéthyl ou sulfopropyl, des groupes esters tels que des groupes d'ester d'acide acétique, d'acide β-aminopropionique, d'acide glycolique ou d'acide malonique.
  10. Utilisation ou procédé selon l'une des revendications précédentes, caractérisé(e) en ce que, dans le carbamate de cellulose, le degré de substitution, rapporté à la proportion en groupes carbamate, se situe dans la plage allant de 0,2 à 2, en particulier de 0,4 à 1,2.
EP14776608.3A 2013-09-24 2014-09-22 Carbamates de cellulose utilisés comme principes actifs ayant la capacité de dissoudre les saletés Not-in-force EP3049508B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201310219183 DE102013219183A1 (de) 2013-09-24 2013-09-24 Cellulosecarbamate als schmutzablösevermögende Wirkstoffe
PCT/EP2014/070072 WO2015044061A1 (fr) 2013-09-24 2014-09-22 Carbamates de cellulose utilisés comme principes actifs ayant la capacité de dissoudre les saletés

Publications (2)

Publication Number Publication Date
EP3049508A1 EP3049508A1 (fr) 2016-08-03
EP3049508B1 true EP3049508B1 (fr) 2018-03-28

Family

ID=51626012

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14776608.3A Not-in-force EP3049508B1 (fr) 2013-09-24 2014-09-22 Carbamates de cellulose utilisés comme principes actifs ayant la capacité de dissoudre les saletés

Country Status (3)

Country Link
EP (1) EP3049508B1 (fr)
DE (1) DE102013219183A1 (fr)
WO (1) WO2015044061A1 (fr)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HUE072325T2 (hu) 2021-08-12 2025-11-28 Procter & Gamble Felületaktív tiszítóanyagot és biológiailag lebomló oltó- polimereket tartalmazó felületaktív készítmény
EP4134421B1 (fr) 2021-08-12 2025-05-21 The Procter & Gamble Company Composition détergente comprenant un tensioactif détergent et un polymère greffé
CN118119692A (zh) 2021-10-14 2024-05-31 宝洁公司 包含阳离子去垢性聚合物和脂肪酶的织物和家庭护理产品
EP4321604A1 (fr) 2022-08-08 2024-02-14 The Procter & Gamble Company Tissu et composition de soins à domicile comprenant un tensioactif et un polyester
WO2024094785A1 (fr) 2022-11-04 2024-05-10 Clariant International Ltd Polyesters
WO2024094802A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Tissu et composition d'entretien ménager
EP4612209A1 (fr) 2022-11-04 2025-09-10 The Procter & Gamble Company Composition d'entretien textile et ménager
EP4630526A1 (fr) 2022-12-05 2025-10-15 The Procter & Gamble Company Composition de soin textile et ménager comprenant un composé de carbonate de polyalkylène
EP4634352A1 (fr) 2022-12-12 2025-10-22 The Procter & Gamble Company Composition de soin textile et ménager
EP4386074B1 (fr) 2022-12-16 2025-12-03 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4458932A1 (fr) 2023-05-04 2024-11-06 The Procter & Gamble Company Tissu et composition de soins à domicile
EP4458933A1 (fr) 2023-05-05 2024-11-06 The Procter & Gamble Company Composition de tissu et de soins à domicile comprenant un polyol propoxylé
EP4484536A1 (fr) 2023-06-26 2025-01-01 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4549540A1 (fr) 2023-11-02 2025-05-07 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4549541A1 (fr) 2023-11-02 2025-05-07 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4553137A1 (fr) 2023-11-08 2025-05-14 The Procter & Gamble Company Composition de soin domestique et de tissu comprenant un polyester
EP4570892A1 (fr) 2023-12-15 2025-06-18 The Procter & Gamble Company Composition de détergent à lessive
EP4570893A1 (fr) 2023-12-15 2025-06-18 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4610340A1 (fr) 2024-03-01 2025-09-03 The Procter & Gamble Company Composition de détergent à lessive comprenant un polyester
EP4624555A1 (fr) 2024-03-26 2025-10-01 The Procter & Gamble Company Compositions de soin pour tissus et maisons
EP4624554A1 (fr) 2024-03-26 2025-10-01 The Procter & Gamble Company Compositions d'entretien de tissus
EP4636063A1 (fr) 2024-04-19 2025-10-22 The Procter & Gamble Company Produit détergent à lessive à dose unitaire
EP4663732A1 (fr) 2024-06-10 2025-12-17 The Procter & Gamble Company Utilisation de polymère greffé dans une composition de détergent pour lessive
EP4663733A1 (fr) 2024-06-10 2025-12-17 The Procter & Gamble Company Utilisation d'un polymère greffé dans un procédé de blanchissage

Family Cites Families (12)

* 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
US4000093A (en) 1975-04-02 1976-12-28 The Procter & Gamble Company Alkyl sulfate detergent compositions
US4136038A (en) 1976-02-02 1979-01-23 The Procter & Gamble Company Fabric conditioning compositions containing methyl cellulose ether
GB8519047D0 (en) 1985-07-29 1985-09-04 Unilever Plc Detergent composition
GB8519046D0 (en) 1985-07-29 1985-09-04 Unilever Plc Detergent compositions
CA2345573C (fr) 1998-09-30 2011-08-09 Unilever Plc Traitement pour textiles
GB9821217D0 (en) 1998-09-30 1998-11-25 Unilever Plc Treatment for substrates
GB0007654D0 (en) 2000-03-29 2000-05-17 Unilever Plc Laundry treatment for fabrics
GB2360791A (en) 2000-03-29 2001-10-03 Unilever Plc Softening treatment for fabrics
GB2360793A (en) 2000-03-29 2001-10-03 Unilever Plc Improving perfume deposition or retention on fabrics
GB0121148D0 (en) * 2001-08-31 2001-10-24 Unilever Plc Polymers and their use
DE102012003342A1 (de) * 2012-02-21 2013-08-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Waschen mit Fasern

Also Published As

Publication number Publication date
EP3049508A1 (fr) 2016-08-03
WO2015044061A1 (fr) 2015-04-02
DE102013219183A1 (de) 2015-03-26

Similar Documents

Publication Publication Date Title
EP3810742B1 (fr) Carbamates de xylose utilisés comme agents antisalissures
EP3049508B1 (fr) Carbamates de cellulose utilisés comme principes actifs ayant la capacité de dissoudre les saletés
EP3414310B1 (fr) 6-désoxy-6-amino-celluloses utilisées comme agents antisalissures
WO2019243108A1 (fr) Dérivés de chitosane utilisés comme agents antisalissures
WO2019243072A1 (fr) Dérivés de pullulane utilisés comme agents antisalissures
EP2054495B1 (fr) Détergents contenant un dérivé de cellulose à pouvoir de décollement des salissures, actif sur le coton
EP2836580B1 (fr) Cellulose microfibrillaire en tant que substance active à pouvoir détachant
EP1592766B1 (fr) Procede pour renforcer la puissance de nettoyage de produits de lavage au moyen d'une combinaison de derives de cellulose
EP1888733B1 (fr) Renforcement de l'activite nettoyante de lessives par l'intermediaire de polymeres
EP1592763B2 (fr) Detergent contenant un agent de blanchiment et un derive de cellulose facilitant l'elimination des salissures sur les textiles en coton
EP1592765B1 (fr) Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique
EP1592764B1 (fr) Augmentation de la capacite d'absorption d'eau de textiles
EP3083918B1 (fr) Copolymères comprenant des groupes siloxane, utilisés comme agents antisalissures
EP1888732B1 (fr) Renforcement du pouvoir detersif de detergents par l'intermediaire d'un polymere
EP2917319B1 (fr) Polymères comportant des groupes polaires, servant de substances actives à pouvoir détachant
DE10351322A1 (de) Bleichmittelhaltiges Waschmittel mit baumwollaktivem schmutzablösevermögendem Cellulosederivat
DE102015003483A1 (de) Polymere Ester aromatischer Dicarbonsäuren als schmutzablösevermögende Wirkstoffe
DE102014206987A1 (de) Glycerinesterderivate als schmutzablösevermögende Wirkstoffe

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: 20160331

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

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HEINZE, THOMAS

Inventor name: STROTZ, MICHAEL

Inventor name: KROPF, CHRISTIAN

Inventor name: JANSSEN, FRANK

Inventor name: JUNKES, CHRISTA

Inventor name: GANSKE, KRISTIN

Inventor name: JOB, MAREILE

RIN1 Information on inventor provided before grant (corrected)

Inventor name: JANSSEN, FRANK

Inventor name: HEINZE, THOMAS

Inventor name: JOB, MAREILE

Inventor name: KROPF, CHRISTIAN

Inventor name: STROTZ, MICHAEL

Inventor name: GANSKE, KRISTIN

Inventor name: JUNKES, CHRISTA

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: 20171213

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

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

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: 983444

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: 502014007778

Country of ref document: DE

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

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: 20180628

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: 20180328

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: 20180328

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: 20180328

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20180328

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: 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: 20180629

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: 20180328

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: 20180628

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: 20180328

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: 20180328

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

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

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: 20180328

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

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: 20180328

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: 20180328

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: 20180328

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: 20180328

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: 20180328

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: 20180328

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: 20180328

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

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: 20180328

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: 20180328

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: 20180328

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: 20180730

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502014007778

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: 20180328

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

26N No opposition filed

Effective date: 20190103

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: 20180328

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: 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: 20180328

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180930

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: LU

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

Effective date: 20180922

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: 20180922

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: 20180930

Ref country code: BE

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

Effective date: 20180930

Ref country code: CH

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

Effective date: 20180930

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: 20180328

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

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: 20140922

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: 20180328

Ref country code: MK

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

Effective date: 20180328

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: 20180728

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 983444

Country of ref document: AT

Kind code of ref document: T

Effective date: 20190922

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: 20190922

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: 20230920

Year of fee payment: 10

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

Ref country code: FR

Payment date: 20230928

Year of fee payment: 10

Ref country code: DE

Payment date: 20230920

Year of fee payment: 10

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502014007778

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20240922

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

Ref country code: DE

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

Effective date: 20250401

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

Ref country code: GB

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

Effective date: 20240922

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

Ref country code: FR

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

Effective date: 20240930