EP3194551B1 - Festförmige zusammensetzung für die textilbehandlung - Google Patents

Festförmige zusammensetzung für die textilbehandlung Download PDF

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Publication number
EP3194551B1
EP3194551B1 EP15771063.3A EP15771063A EP3194551B1 EP 3194551 B1 EP3194551 B1 EP 3194551B1 EP 15771063 A EP15771063 A EP 15771063A EP 3194551 B1 EP3194551 B1 EP 3194551B1
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EP
European Patent Office
Prior art keywords
composition
weight
solid composition
acid
compound
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EP15771063.3A
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German (de)
English (en)
French (fr)
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EP3194551A1 (de
Inventor
Matthias Sunder
Patrick Büth
Sheila Edwards
Frank Meier
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL15771063T priority Critical patent/PL3194551T3/pl
Publication of EP3194551A1 publication Critical patent/EP3194551A1/de
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/12—Carbonates bicarbonates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
    • D06L1/04—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents combined with specific additives
    • 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

Definitions

  • the present invention relates to the technical field of textile treatment, in particular textile cleaning or textile washing.
  • the quality of the removal of bleachable soiling such as colored fruit and vegetable stains are a key quality feature of a detergent.
  • the bleachable dirt should be bleached out and / or removed.
  • the textile should not be damaged by the bleach.
  • a solid bleaching agent composition that can be used as an additive should contain few additional ingredients in addition to the bleach-active compound for a careful use of resources.
  • the European patent application EP 0 427 314 A2 describes stable and efficient bleach compositions which contain sodium percarbonate, a bleach activator and an alkali metal bicarbonate, sesquicarbonate, or dihydrogen orthophosphate, and which can be used as a bleach additive or part of a detergent composition.
  • the European patent application EP 2 527 421 A1 relates to water-soluble pouches in unit dosage form comprising a first camera having a powdered composition containing a source of oxygen bleach and a citrate.
  • the same problem can arise with the formulation of a said bleach additive as a single dose in a portion encased by water-soluble material.
  • the water-soluble shell material mostly contains organic compounds which also come into contact with the concentrated solid bleach additive.
  • the object was therefore to provide storage-stable solid compositions which have a high concentration of at least one peroxide compound in combination with at least one organic compound.
  • a further object of the invention was to provide storage-stable portions as a dosage unit for textile treatment which contain a solid composition with a high concentration of peroxide compound, packaged in a water-soluble casing. On contact with water, the said compositions are released from the portion functioning as a dosage unit.
  • the solid compositions with a high bleach content should protect the textiles and improve the washing performance of detergents, in particular liquid detergents, as an additive in the context of a textile wash.
  • compositions according to the invention can be used outstandingly as an additive to detergents, in particular liquid detergents, in textile treatment. The washing performance is increased.
  • a first subject of the invention is therefore a portion for use in textile treatment according to claims 1-9
  • the solid-form composition can contain further optional ingredients in addition to the ingredients that are mandatory.
  • the total amounts are selected from the specified weight amount ranges in such a way that, together with the amounts of the optional ingredients for the said solid composition, based on its total weight, 100% by weight result.
  • a composition is solid if it is in the solid state of aggregation at 25 ° C. and 1013 mbar.
  • a composition is liquid if it is in the liquid state of aggregation at 25 ° C. and 1013 mbar.
  • a chemical compound is an organic compound if the molecule of the chemical compound contains at least one covalent bond between carbon and hydrogen.
  • a chemical compound is an inorganic compound if the molecule of the chemical compound does not contain a covalent bond between carbon and hydrogen.
  • This definition applies, among other things, to inorganic peroxide compounds as a chemical compound mutatis mutandis.
  • a peroxide compound is a chemical compound that contains the peroxo atom group -O-O- as a structural fragment.
  • the average molar masses given in the context of this application for polymeric ingredients are - unless explicitly stated otherwise - always weight-average molar masses M w , which can basically 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 solid composition according to the invention is formed from a plurality of solid particles.
  • Such an embodiment of the solid composition is preferably in the form of a powder or granules.
  • Said solid particles in turn preferably have a particle diameter X 50.3 (volume average) in a range from 100 to 1500 ⁇ m.
  • X 50.3 volume average
  • These particle sizes can be determined by sieving or by means of a Camsizer particle size analyzer from Retsch.
  • the solid composition according to the invention necessarily contains a defined amount of peroxide compound. It has been found to be preferred according to the invention if the solid composition according to the invention contains peroxide compounds in a total amount of 20 to 50% by weight, in particular 25 to 45% by weight, based on the total weight of the composition.
  • the peroxide compound is selected from at least one inorganic peroxide compound.
  • Suitable peroxide compounds are, in particular, percarbonate compounds, perborate compounds, peroxodisulfate compounds, hydrogen peroxide, addition compounds of hydrogen peroxide with inorganic compounds, organic peroxy acids or mixtures of at least two of these compounds.
  • the peroxide compound is selected from sodium percarbonate, sodium perborate, sodium peroxodisulfate or mixtures thereof.
  • Sodium percarbonate is a particularly preferred peroxide compound.
  • Sodium percarbonate is an addition compound of hydrogen peroxide on sodium carbonate with the formula y Na 2 CO 3 ⁇ xH 2 O 2 , where x is the amount of hydrogen peroxide per y mole of Na 2 CO 3 .
  • Most preferred is the peroxide compound Na 2 CO 3 ⁇ 1.5 H 2 O 2 with the CAS number 15630-89-4.
  • the peroxide compound used according to the invention preferably has an active oxygen content of between 9.0% and 15.0%, in particular from 10.0% to 14.0% (each measured by titration with potassium permanganate).
  • the peroxide compound is in particulate form, in particular as a powder or granulate. It is again preferred if the particles (for example the powder or granules) containing the peroxide compound have a bulk density of 0.70 to 1.30 kg / dm 3 , particularly preferably a bulk density of 0.85 to 1.20 kg / dm 3 (e.g. each measured according to ISO 697).
  • those peroxide compounds are preferably suitable whose particles have an average particle size (volume average) X 50.3 of 0.40 to 0.95 mm, in particular from 0.50 to 0.90 mm (for example measured with a sieve analysis or by a Particle size analyzer Camsizer, Retsch).
  • a solid peroxide compound, in particular sodium percarbonate can be provided with a coating on the surface for additional protection against decomposition.
  • the coating should protect against decomposition of the percarbonate.
  • Water-soluble passivating agents such as, for example, sodium hydrogen carbonate, sodium carbonate, sodium sulfate or metaborate compounds, are preferably suitable as coating agents.
  • the solid peroxide compound, in particular sodium percarbonate is coated on the surface with at least sodium sulfate.
  • the solid peroxide compound has an average particle size X 50.3 of 0.40 to 0.95 mm, in particular from 0.50 to 0.90 mm (e.g. measured with sieve analysis or by a Camsizer particle size analyzer, Retsch company) and are coated with sodium sulfate.
  • Sodium percarbonate particles with a sodium hydrogen carbonate coating obtainable by a surface reaction and their production in a fluidized bed reactor are known to the person skilled in the art from the publication EP 1 227 063 A2 known. Said sodium hydrogen carbonate coatings, however, are undesirable in production due to further technical process steps involving the input of energy.
  • the peroxide compound used can be treated with a phlegmatization agent, in particular with a metaborate compound (the composition according to the invention advantageously contains based on phlegmatization (ie reduction or prevention of possible heat generation due to exothermic decomposition of the solid peroxide compound) on the content of peroxide compound 50 to 100% by weight peroxide compound coated with metaborate), be coated.
  • a phlegmatization agent in particular with a metaborate compound
  • the composition according to the invention advantageously contains based on phlegmatization (ie reduction or prevention of possible heat generation due to exothermic decomposition of the solid peroxide compound) on the content of peroxide compound 50 to 100% by weight peroxide compound coated with metaborate), be coated.
  • the desensitizing coating of the solid peroxide compound is not absolutely necessary, however.
  • composition according to the invention necessarily contains a total amount of 10 to 20% by weight of one or more organic bleach activators, the composition comprising 10 to 20% by weight of one or more organic bleach activators selected from compounds of the multiply N-acylated organic amines. It is preferred if the compositions according to the invention contain a total amount of organic bleach activators, in particular selected from compounds of the multiply N-acylated organic amines, from 11 to 18% by weight, particularly preferably from 12 to 16% by weight, again preferably from 10 to 15% by weight, very particularly preferably from 11 to 14% by weight.
  • Preferred organic bleach activators are compounds from the group of multiply N-acylated organic amines which, under perhydrolysis conditions, give peroxycarboxylic acids (in particular aliphatic peroxycarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms) and / or optionally substituted perbenzoic acid , used.
  • peroxycarboxylic acids in particular aliphatic peroxycarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms
  • perbenzoic acid used.
  • the aforementioned total amounts apply mutatis mutandis to these special organic bleach activators.
  • Perhydrolysis is known to the person skilled in the art as a reaction in which, in a protic solvent (e.g. water), an anion - OOH binds covalently to a reactant RX by nucleophilic substitution to give the compound ROOH and the splitting off of a leaving group X with lysis of the chemical bond between R and X causes.
  • a protic solvent e.g. water
  • the organic bleach activators comprise at least one compound from the group of the multiply N-acylated organic amines, these being preferably those which form aliphatic peroxycarboxylic acids under perhydrolysis conditions.
  • the aforementioned total amounts apply mutatis mutandis to these special organic bleach activators.
  • acylated alkylenediamines in particular tetraacetyl-ethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT)
  • acylated glycolurils especially tetraacetylglycoluril (TAGU)
  • N-acylimides especially N-nonanoylsuccinimide (NOSI)
  • acylated phenol sulfonates especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferred.
  • the aforementioned total amounts apply mutatis mutandis to these special organic bleach activators.
  • the solid composition necessarily contains a defined amount of hydrogen carbonate, calculated as sodium hydrogen carbonate.
  • hydrogen carbonate is to be understood as a chemical compound which contains at least one hydrogen carbonate ion (HCO 3 - ) before the composition according to the invention is produced and which is different from peroxide compounds according to the invention.
  • the amount by weight of hydrogen carbonate in the composition according to the invention is expressed according to the definition as the equivalent amount by weight of sodium hydrogen carbonate.
  • compositions which, based on the total weight of the composition, contain hydrogen carbonate in a total amount of 7.5 to 30% by weight, calculated as sodium hydrogen carbonate, are preferred according to the invention.
  • hydrogen carbonate from sodium hydrogen carbonate, potassium hydrogen carbonate or mixtures thereof.
  • Sodium hydrogen carbonate is very particularly preferably suitable as the hydrogen carbonate.
  • the particles (for example the powder or granules) containing hydrogen carbonate have a bulk density of 0.40 to 1.50 kg / dm 3 , particularly preferably a bulk density of 0.90 to 1.10 kg / dm 3 ( eg each measured according to ISO 697).
  • the particles (for example the powder or granules) containing the peroxide compound have a bulk density of 0.70 to 1.30 kg / dm 3 , particularly preferably a bulk density of 0, 85 to 1.20 kg / dm 3 (for example each measured according to ISO 697).
  • the solid composition necessarily contains a defined amount by weight of organic compound.
  • the composition according to the invention contains, based on its total weight, organic compounds in a total amount of 20.0% by weight to 35.0% by weight.
  • the technical effect is particularly pronounced when at least one organic compound is used which contains at least one carbon atom with an oxidation number of + II to -II, to which at least one atom which is different from carbon and hydrogen is covalently bonded.
  • organic compounds include the mandatory organic bleach activator.
  • compositions according to the invention preferably contain at least one organic graying inhibitor as an organic compound.
  • a graying inhibitor is a chemical compound that prevents or restricts the re-deposition of the dirt dispersed in the washing liquor on the textile.
  • the graying inhibitor is preferably present in the composition according to the invention in a total amount of 0.2 to 12.0% by weight, in particular from 1.0 to 10.0% by weight, very particularly preferably from 2.5 to 9.5% by weight. %, each based on the weight of said composition.
  • the solid compositions contain, as an organic graying inhibitor, a polymeric compound which carries at least two anionic groups.
  • Preferred anionic groups are selected from carboxylate, sulfonate, sulfate or mixtures thereof.
  • the solid composition contains at least one graying-inhibiting polysaccharide as an organic compound.
  • the liquid washing or cleaning agent preferably contains methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose (CMC), an ester sulfonic acid salt of cellulose, a monosulfonic acid salt of cellular acid, a sulfuric acid salt of starch Starch or a mixture of at least two of these graying-inhibiting polysaccharides.
  • Carboxymethyl cellulose, in particular sodium carboxymethyl cellulose is very particularly preferably contained in the compositions according to the invention as the graying-inhibiting polysaccharide.
  • the preferred total amount of graying-inhibiting polysaccharide, in particular of carboxymethyl cellulose, is 0.2 to 12.0% by weight, in particular from 1.0 to 10.0% by weight, very particularly preferably from 2.5 to 9.5% by weight. %, each based on the weight of the said composition.
  • the solid composition contains at least one soil-release active ingredient as the organic compound.
  • soil release agents Substances are often referred to as “soil-release” active ingredients or, because of their ability to make the treated surface, for example the fiber, dirt-repellent, as “soil repellents". Because of their chemical similarity to polyester fibers, particularly effective soil-releasing active ingredients, which can also show the desired effect on fabrics made of other materials, are copolyesters that contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-release polyesters of the type mentioned and their use in detergents have been known for a long time.
  • polymers made from ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights from 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents in Germany Patent specification DE 28 57 292 described.
  • the European patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
  • polyesters which, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and are end group-capped with C 1 - to C 4 -alkyl groups are.
  • the European patent specification EP 253 567 relates to soil-release polymers with a molecular weight of 900 to 9000 made from ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights from 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 0.6 to 0.95.
  • EP 272 033 are known at least partially by C 1-4 -alkyl or acyl groups end-capped polyesters with polypropylene terephthalate and polyoxyethylene terephthalate units.
  • the European patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters.
  • EP 357 280 sulfonation of unsaturated terminal groups, soil-release polyesters containing terephthalate, alkylene glycol and poly-C 2 - 4 prepared glycol units.
  • polyesters can be obtained, for example, by polycondensation of dialkyl terephthalate, dialkyl 5-sulfoisophthalate, alkylene glycols, optionally polyalkylene glycols (if a, b and / or c> 1) and polyalkylene glycols end-capped at one end (corresponding to unit III). It should be pointed out that for numbers a, b, c> 1 there is a polymeric structure and thus the coefficients can assume any value in the given interval as a mean value. This value reflects the number average molecular weight.
  • the structures can contain, for example, 1 to 50 units (I) per polymer chain.
  • a suitable unit (II) is an ester of 5-sulfoisophthalic acid with one or more difunctional, aliphatic alcohols; the aforementioned are preferably used here.
  • 1 to 50 units (II) can be present in the structures.
  • the preferred amount of the structural unit used is ( III) that which is necessary to achieve the average molecular weights described below.
  • crosslinked or branched polyester structures are also used according to the invention. This is expressed by the presence of a crosslinking polyfunctional structural unit (IV) with at least three to a maximum of 6 functional groups capable of the esterification reaction. Acid, alcohol, ester, anhydride or epoxy groups, for example, can be named as functional groups. Different functionalities are also possible in one molecule.
  • Citric acid malic acid, tartaric acid and gallic acid, particularly preferably 2,2-dihydroxymethylpropionic acid
  • polyhydric alcohols such as pentaerythrol, glycerol, sorbitol and / or trimethylolpropane can be used.
  • It can also be polybasic aliphatic or aromatic carboxylic acids, such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), or benzene-1,3,5-tricarboxylic acid ( Trimesitic acid) act.
  • the weight fraction of crosslinking monomers can be up to 10 wt .-%, in particular up to 5 wt .-% and particularly preferably up to 3 wt .-%.
  • the polyesters containing the structural units (I), (II) and (III) and optionally (IV) generally have number average molecular weights in the range from 700 to 50,000 g / mol, the number average molecular weight being determined by means of size exclusion chromatography in aqueous solution using a calibration with the aid of narrowly distributed polyacrylic acid sodium salt standards.
  • the number average molecular weights are preferably in the range from 800 to 25,000 g / mol, in particular 1,000 to 15,000 g / mol, particularly preferably 1,200 to 12,000 g / mol.
  • solid polyesters which have softening points above 40 ° C. are preferably used as a constituent of the second type of particle; they preferably have a softening point between 50 and 200.degree. C., particularly preferably between 80.degree. C. and 150.degree. C. and extremely preferably between 100.degree. C. and 120.degree.
  • the polyesters can be synthesized by known processes, for example by first heating the abovementioned components with the addition of a catalyst at normal pressure and then building up the required molecular weights in vacuo by distilling off excess stoichiometric amounts of the glycols used.
  • the known transesterification and condensation catalysts such as titanium tetraisopropoxide, dibutyltin oxide, alkali or alkaline earth metal alcoholates or antimony trioxide / calcium acetate are suitable for the reaction.
  • EP 442 101 see EP 442 101 referred.
  • Polyesters used with preference have a solid consistency and can be easily ground to powder or compacted or agglomerated to give granules of defined particle sizes.
  • the granulation can be carried out in such a way that the copolymers obtained as a melt during the synthesis are solidified into flakes or flakes by cooling in a cool gas stream, for example air or nitrogen, or by application to a flaking roller or a treadmill.
  • This coarse material can optionally be further ground, for example, in the roller frame or in the sieve mill, which can be followed by sieving and rounding as described above.
  • the granulation can also take place in such a way that the polyesters are ground to powder after solidification and then converted into granulates with defined particle sizes by compacting or agglomeration and the rounding described above.
  • the solid composition contains at least one enzyme as the organic compound.
  • all enzymes established in the prior art for textile treatment can be used in this regard. It is preferably one or more enzymes that can develop catalytic activity in a detergent, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-splitting enzyme, tannase, xylanase, xanthanase, ⁇ -glucosidase, carrageenase, perhydrolase , Oxidase, oxidoreductase and their mixtures.
  • Preferred hydrolytic enzymes include, in particular, proteases, amylases, in particular ⁇ -amylases, cellulases, lipases, Hemicellulases, in particular pectinases, mannanases, ⁇ -glucanases, and mixtures thereof.
  • proteases amylases, in particular ⁇ -amylases, cellulases, lipases, Hemicellulases, in particular pectinases, mannanases, ⁇ -glucanases, and mixtures thereof.
  • proteases are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are accordingly preferred.
  • subtilisin type those of the subtilisin type are preferred.
  • these are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilases, but no longer the subtilisins in the narrower sense of the term, thermitase, proteinase K and the enzymes Proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark.
  • subtilisins 147 and 309 are sold by the Novozymes company under the trade names Esperase® and Savinase®, respectively.
  • the protease variants under the name BLAP® are derived from the protease from Bacillus lentus DSM 5483.
  • proteases that can be used are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which are sold under the trade names Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, sold under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, sold under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, sold under the trade name Proleather ® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • the proteases from Bacillus gibsonii and Bacillus pumilus are also particularly preferably used.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their improved further developments for use in detergents or cleaning agents.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl® and from Genencor under the name Purastar®ST. Further development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl® and Termamyl®ultra, from Genencor under the name Purastar®OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®.
  • the ⁇ -amylase from B. amyloliquefaciens is marketed by the Novozymes company under the name BAN®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG® and Novamyl®, also by the Novozymes company. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be emphasized. Fusion products of all mentioned molecules can also be used.
  • lipases or cutinases which can be used according to the invention and which are contained in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors, are the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed lipases, especially those with the amino acid substitution D96L. They are sold, for example, by the Novozymes company under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, for example, the cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can be used.
  • Lipases which can also be used are available from Amano under the names Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML® available.
  • the lipases or cutinases from the Genencor company can be used whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Lipase® and Lipomax® originally marketed by Gist-Brocades and the enzymes sold by Meito Sangyo KK, Japan under the names Lipase MY-30®, Lipase OF® and Lipase PL® Mention should also be made of the product Lumafast® from Genencor.
  • cellulases can be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects.
  • performance aspects include, in particular, the contributions of the cellulase to the primary washing performance of the agent (cleaning performance), to the secondary washing performance of the agent (anti-redeposition effect or graying inhibition), to finishing (tissue effect) or to exerting a "stone washed" effect.
  • cleaning performance the contributions of the cellulase to the primary washing performance of the agent
  • anti-redeposition effect or graying inhibition to finishing (tissue effect) or to exerting a "stone washed" effect.
  • EG endoglucanase
  • a useful fungal, endoglucanase (EG) -rich cellulase preparation, or further developments thereof, is offered by the Novozymes company under the trade name Celluzyme®.
  • Endolase® and Carezyme® are based on the 50 kD EG or the 43 kD EG from H. insolens DSM 1800.
  • Other commercial products from this company that can be used are Cellusoft®, Renozyme® and Celluclean®.
  • the 20 kD EG from Melanocarpus which are available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, can also be used.
  • Further commercial products from AB Enzymes are Econase® and Ecopulp®.
  • Further suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, the ones from Bacillus sp.
  • Cellulases are Thielavia terrestris cellulase variants, cellulases from Melanocarpus, in particular Melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.
  • hemicellulases can be used in particular to remove certain problematic soiling.
  • these include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-splitting enzymes and ⁇ -glucanases.
  • the ⁇ -glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes.
  • Hemicellulases which are particularly preferred according to the invention are mannanases which are sold, for example, under the trade name Mannaway® by the Novozymes company or Purabrite® by the Genencor company.
  • the pectin-splitting enzymes also include enzymes with the designations pectinase, pectate lyase, pectin esterase, pectin demethoxylase, pectin methoxylase, pectin methylesterase, pectin methylesterase, pectin methylesterase, pectinolactinase, pectinolactinase, pectinolactinase, pectinolactinase, pectinolactinase, pectongalactinase, pectopolyhydrolase, pectin-pectylin EndoPolygalacturonase, poly- ⁇ -1,4-galacturonid glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1,4- ⁇ -galacturonidase, exopolygalactu
  • enzymes suitable in this regard are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from the Novozymes company, under the names 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.
  • the solid compositions contain enzymes preferably in total amounts of 1 ⁇ 10 -8 to 5 percent by weight, based on active protein.
  • the enzymes are preferred in a total amount of 0.001 to 4% by weight, more preferably from 0.01 to 3% by weight, even more preferably from 0.05 to 1.25% by weight and particularly preferably from 0, 2 to 1.0 wt .-% contained in these agents.
  • organic surfactants organic builders, organic complexing agents, organic optical brighteners, organic pH adjusters, perfumes, organic dyes, organic dye transfer inhibitors or mixtures thereof can be contained in the solid composition as organic compounds.
  • the solid composition should preferably be used as an additive in the context of a textile wash. For this reason, the solid composition necessarily contains 0 to 5% by weight of surfactant (ie no surfactant up to a maximum of 5% by weight of surfactant), preferably 0 to 4% by weight, particularly preferably 0 to 3.5% by weight , Contains surfactant.
  • soap is the water-soluble sodium or potassium salts of saturated and unsaturated fatty acids with 10 to 20 carbon atoms, the resin acids of rosin (yellow resin soaps) and naphthenic acids, which are used as solid or semi-solid mixtures mainly for washing and cleaning purposes.
  • Sodium or potassium salts of saturated and unsaturated fatty acids with 10 to 20 carbon atoms, in particular with 12 to 18 carbon atoms, are preferred soaps according to the invention.
  • Particularly preferred compositions are characterized in that they - based on their weight - 0.1 to 4.0% by weight, particularly preferably 0.5 to 3.5% by weight, very particularly preferably 1.0 to 3 Contain 0% by weight soap (s).
  • the solid compositions contain no nonionic surfactant.
  • Organic builders which can be present in the solid composition are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these.
  • Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g / mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molar masses from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, can be preferred.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • An organic optical brightener is preferably selected from the substance classes of the distyrylbiphenyls, the stilbenes, the 4,4'-diamino-2,2'-stilbene disulfonic acids, the coumarins, the dihydroquinolinones, the 1,3-diarylpyrazolines, the naphthalic acid imides and the benzoxazole systems , the benzisoxazole systems, the benzimidazole systems, the pyrene derivatives substituted by heterocycles and mixtures thereof.
  • organic optical brighteners include disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulfonate (available for example as Tinopal® DMS from BASF SE), disodium-2,2 '-bis- (phenyl-styryl) disulfonate (available for example as Tinopal® CBS from BASF SE), 4,4'-bis [(4-anilino-6- [bis (2-hydroxyethyl) amino] -1.3, 5-triazin-2-yl) amino] stilbene-2,2'-disulfonic acid (available for example as Tinopal® UNPA from BASF SE), hexasodium-2,2 '- [vinylenbis [(3-sulphonato-4,1-phenylene) ) imino [6- (diethylamino) -1,3,5-triazine-4,2-diyl] imino]]] bis (benzen
  • the organic dye transfer inhibitor be a polymer or copolymer of cyclic amines such as vinyl pyrrolidone and / or vinyl imidazole.
  • Polymers suitable as color transfer inhibitors include polyvinyl pyrrolidone (PVP), polyvinyl imidazole (PVI), copolymers of vinyl pyrrolidone and vinyl imidazole (PVP / PVI), polyvinyl pyridine-N-oxide, poly-N-carboxymethyl-4-pyridium chloride, polyethylene glycol-modified copolymers of vinyl pyridolazole and mixtures thereof.
  • Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) are particularly preferably used as color transfer inhibitors.
  • the polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53 available.
  • the copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000.
  • a PVP / PVI copolymer is commercially available, for example from BASF under the name Sokalan® HP 56.
  • Another extremely preferred color transfer inhibitor are polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, from BASF under the name Sokalan® HP 66 are.
  • the solid composition based on its total weight, is solid, basic silicate (calculated as water glass), in a total amount of at most 20.0% by weight, in particular of at most 15.0% by weight. %, contains.
  • the solid composition is very particularly preferably free from solid, basic silicate.
  • the solid composition is made by mixing the raw materials.
  • a batch process or a continuous mixing process can be used here.
  • Tumble mixers, paddle mixers (Forberg, Lödige, Gericke) or helix mixers (Amixon, Ruberg brothers) are particularly suitable as mixing devices.
  • the ingredients of the solid composition according to the invention are mixed with little energy input; in particular, mixing tools are used which mix at a peripheral speed of 0.1 to 5 m / s.
  • the solid composition is ideally suited for packaging in a water-soluble portion.
  • the solid composition is in a chamber formed from water-soluble material.
  • the water-soluble material forms walls of the chamber and thereby envelops the solid composition.
  • the portion according to the invention is an independent metering unit with at least two chambers in which the material to be metered is contained.
  • a chamber is a space delimited by walls (e.g. by a film), which can also exist without the material to be dosed (possibly with a change in its shape).
  • a layer of a surface coating therefore explicitly does not fall under the definition of a wall.
  • the walls of the chambers are made of a water-soluble material.
  • the water solubility of the material can be determined with the help of a square film of the said material (film: 22 ⁇ 22 mm with a thickness of 76 ⁇ m) fixed in a square frame (edge length on the inside: 20 mm). Said framed film is immersed in 800 mL of distilled water at a temperature of 20 ° C.
  • the material should dissolve with stirring (stirring speed, magnetic stirrer 300 rpm, stirring rod: 6.8 cm long, diameter 10 mm) within 600 seconds in such a way that no individual solid film particles are visible to the naked eye.
  • the walls are preferably made of a water-soluble film. According to the invention, this film can preferably have a thickness of at most 150 ⁇ m (particularly preferably of at most 120 ⁇ m). Preferred walls are accordingly made from a water-soluble film and have a thickness of at most 150 ⁇ m (particularly preferably of at most 120 ⁇ m, very particularly preferably of at most 90 ⁇ m).
  • the portion preferably contains the solid composition in a total amount from 4.0 to 10.0 g, in particular from 5.0 to 9.0 g.
  • Both anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants can be used as the surfactant of the first composition. It is preferred according to the invention if the first composition of the portion contains at least one anionic surfactant and at least one nonionic surfactant.
  • Sulfonates and / or sulfates can preferably be used as the anionic surfactant.
  • the content of anionic surfactant is 5 to 25% by weight and preferably 8 to 20% by weight, based in each case on the total first or second liquid, low-water detergent or cleaning agent.
  • Surfactants of the sulfonate type are preferably C 9-13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C 12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is possible.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • the alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred.
  • the C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and also C 14 -C 15 -alkyl sulfates are preferred.
  • 2,3-Alkyl sulfates are also suitable anionic surfactants.
  • fatty alcohol ether sulfates such as the sulfuric acid monoesters of straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 -18 fatty alcohols with 1 to 4 EO are suitable.
  • Suitable anionic surfactants are soaps.
  • Saturated and unsaturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, are suitable.
  • the anionic surfactants and the soaps can be in the form of their sodium, potassium or magnesium or ammonium salts.
  • the anionic surfactants are preferably in the form of their ammonium salts.
  • Preferred counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.
  • the first composition contains an alkylbenzenesulfonic acid neutralized with monoethanolamine, in particular C 9-13 -alkylbenzenesulfonic acid, and / or a fatty acid neutralized with monoethanolamine.
  • Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides and mixtures thereof.
  • the nonionic surfactant used is preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 4 EO or 7 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 5 EO, 7 EO or 8 EO, C 12-18 - Alcohols with 5 EO or 7 EO and mixtures of these.
  • the stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be an integer or a fraction.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol for example a mixture of a C 16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO, are also suitable.
  • the first composition particularly preferably contains a C 12-18 fatty alcohol with 7 EO, a C13-15 oxo alcohol with 7 EO and / or a C13-15 oxo alcohol with 8 EO as the nonionic surfactant.
  • the content of nonionic surfactant is 1 to 25% by weight and preferably 2 to 20% by weight, based in each case on the total first composition.
  • the total amount of surfactant in the first composition is 40 to 75% by weight and preferably 50 to 70% by weight, based in each case on the total first composition.
  • the first composition additionally contains at least one polyalkoxylated polyamine.
  • the polyalkoxylated polyamine in the context of the present invention and its individual aspects is a polymer with an N-atom-containing backbone which carries polyalkoxy groups on the N-atoms.
  • the polyamine has primary amino functions at the ends (terminus and / or side chains) and preferably both secondary and tertiary amino functions in the interior; if appropriate, it can also have only secondary amino functions 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 preferably has an average molar mass in the range from 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol.
  • the N atoms in the polyamine are separated from one another by alkylene groups, preferably by alkylene groups having 2 to 12 carbon atoms, in particular 2 to 6 carbon atoms, not all alkylene groups having to have the same number of carbon atoms.
  • Ethylene groups, 1,2-propylene groups, 1,3-propylene groups and mixtures thereof are particularly preferred.
  • Polyamines which carry ethylene groups as said alkylene group are also referred to as polyethyleneimine or PEI.
  • PEI is a polymer which is particularly preferred according to the invention and has a backbone containing N atoms.
  • the primary amino functions in the polyamine can have 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function has to be alkoxy-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 50.
  • the alkoxy groups in the polyalkoxylated polyamine are preferably polypropoxy groups that are bonded directly to N atoms and / or Polyethoxy groups which are bound to any propoxy radicals that may be present and to N atoms which do not carry any propoxy groups.
  • Polyethoxylated polyamines are obtained by reacting polyamines with ethylene oxide (EO for short).
  • EO ethylene oxide
  • the polyalkoxylated polyamines which contain ethoxy and propoxy groups can preferably be obtained by reacting polyamines with propylene oxide (PO for short) and then reacting with ethylene oxide.
  • PO propylene oxide
  • the average number of propoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 40, in particular 5 to 20,
  • the average number of ethoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 10 to 60, in particular 15 to 30.
  • Polyalkoxysubstituenten in polyalkoxylated polyamine may partially or completely with a C 1 - be etherified alkyl group - C 10, in particular C 1 -C. 3
  • Polyalkoxylated polyamines which are particularly preferred according to the invention can be selected from polyamines reacted with 45EO per primary and secondary amino function, PEIs reacted with 43EO per primary and secondary amino function, PEIs reacted with 15EO + 5PO per primary and secondary amino function, PEIs reacted with 15PO + 30EO per primary and secondary amino function secondary amino function, PEI's reacted with 5PO + 39.5EO per primary and secondary amino function, PEI's reacted with 5PO + 15EO per primary and secondary amino function, PEI's reacted with 10PO + 35EO per primary and secondary amino function, PEI's reacted with 15PO + 30EO per primary and secondary amino function and PEI's reacted with 15PO + 5EO per primary and secondary amino function.
  • a very particularly preferred alkoxylated polyamine is PEI with a content of 10 to 20 nitrogen atoms reacted with 20 units of EO per primary or secondary amino function of the polyamine.
  • polyalkoxylated polyamines which are obtainable by reacting polyamines with ethylene oxide and, if appropriate, additionally propylene oxide. If polyalkyoxylated polyamines with ethylene oxide and propylene oxide are used, the proportion of propylene oxide in the total amount of alkylene oxide is preferably 2 mol% to 18 mol%, in particular 8 mol% to 15 mol%.
  • the first composition contains polyalkoxylated polyamines preferably in a total amount of 0.5 to 10% by weight, in particular 1.0 to 7.5% by weight.
  • the first composition made up in the water-soluble portion in the first chamber can contain water, in which case, in particular for liquid first compositions, the content of water based on the entire first composition is not more than 20% by weight, preferably not more than 15% by weight, amounts.
  • the water content is determined using the Karl Fischer method.
  • the first composition can contain further ingredients which further improve the performance and / or aesthetic properties of the first composition.
  • the first composition preferably additionally contains one or more substances from the group of builders, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, anti-enema agents, anti-crease agents , antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bitter agents, ironing aids, phobic and impregnating agents, skin-care agents, swelling and anti-slip agents, softening components and UV absorbers.
  • the portion necessarily comprises water-soluble material for forming the delimiting wall of the at least one chamber.
  • the water-soluble material is preferably formed by a water-soluble film material.
  • Such water soluble servings can be made by either vertical form fill sealing (VFFS) or thermoforming processes.
  • VFFS vertical form fill sealing
  • the thermoforming process generally includes forming a first layer of a water soluble sheet material to form at least one recess for receiving it at least one composition in each case, filling the composition into the respective bulge, covering the bulges filled with the composition with a second layer of a water-soluble film material and sealing the first and second layers together at least around the bulges.
  • the water-soluble material preferably contains at least one water-soluble polymer.
  • the water-soluble material preferably contains a water-soluble film material selected from polymers or polymer mixtures.
  • the envelope can be formed from one or from two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and of the further layers, if present, can be the same or different.
  • the water-soluble material contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Suitable water-soluble films as water-soluble material are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 to 1,000,000 gmol- 1 , preferably from 20,000 to 500,000 gmol- 1 , particularly preferably from 30,000 to 100,000 gmol- 1 and in particular from 40,000 to 80,000 gmol -1 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble material comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • Polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and / or mixtures of the above polymers can also be added to the film material suitable as water-soluble material.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include vinyl alcohol as well as an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof in addition to vinyl alcohol.
  • Suitable water-soluble films for use as the water-soluble material of the water-soluble potion according to the invention are films which are sold under the name Monosol M8630 by MonoSol LLC.
  • Other suitable films include films called Solublon® PT, Solublon® KA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.
  • the portion preferably contains the second composition in a total amount of 4.0 to 10.0 g, in particular 5.0 to 9.0 g.
  • Another subject of the invention is the use of a portion as described herein for textile treatment.
  • Yet another subject matter of the invention is a method for treating textiles, comprising the steps of metering a portion of the first subject matter of the invention to produce a water-containing wash liquor and bringing the resulting wash liquor into contact with textiles.
  • the preferred embodiments described for the first subject matter of the invention also apply mutatis mutandis to the other subject matter of the invention.
  • Table 1 Solid compositions V1 [% by weight] E1 [% by weight] Sodium percarbonate (granules) 47.0 47.0 TAED 13.0 13.0 Carboxymethyl cellulose 6.0 6.0 Sodium bicarbonate - 10.2 Sodium silicate [(Na 2 O) (SiO 2 ) 2.5 ] 10.2 - C18 fatty acid soap 3.0 3.0 Enzymes (protease, lipase, amylase, mannanase) in granules made from sodium sulfate 10.7 10.7 Sodium sulfate ad 100 ad 100
  • the sodium percarbonate granules were mixed with 6 g of sodium sulfate using a known method ( WO 2008/012181 A1 ) homogeneously coated and placed in a tumble mixer. Instead of this coated sodium percarbonate, 53.3% by weight of sodium percarbonate Q35 (contains 88.18% by weight of sodium percarbonate, Evonik) can be initially charged. The remaining components were placed in the tumble mixer and the compositions were prepared by dry mixing the components for 3 minutes at 10 revolutions / minute.
  • the components of the liquid composition were mixed in sequence in a stirred kettle with stirring.
  • a portion P1 according to the invention was provided which contained 8.5 g of the solid composition E1 of Table 1 and 16.5 g of the composition L1 of Table 2.
  • a portion P2 not according to the invention, was provided which contained 8.5 g of the solid composition V1 of Table 1 and 16.5 g of the composition L1 of Table 2.
  • a M8630 film from Monosol (90 ⁇ m) was stretched onto a heatable mold with a double cavity.
  • the stretched film was heated at 105 ° C. for a period of 2400 ms and then drawn into the cavity by a vacuum.
  • a corresponding amount of the solid composition from Table 1 was then pre-weighed into the first cavity and then the amount of the liquid composition L1 from Table 2 was added to the second cavity by means of a syringe.
  • an upper film (M8630, 90 ⁇ m) is placed to close the cavities and is welded to the first film by means of heat (150 ° C, 1000 ms).
  • the portion was removed from the cavity.
  • a wall of the powder chamber of the portion was then perforated with a needle. As a result, excess air escaped from the powder chamber of the portion and the film of the wall relaxed.
  • 325 g of a solid composition were placed in a Dewar vessel with a temperature measuring probe, the sample was heated to 55 ° C. in a heating cabinet and stored.
  • the temperature of the solid composition in the Dewar vessel was measured over a storage period of 250 hours at 55 ° C. and plotted against the storage time.
  • the solid composition V1 not according to the invention showed severe self-decomposition in which the sample heated to more than 61 ° C. within 100 hours and up to 189 ° C. after 140 hours.
  • the self-accelerating decomposition temperature (SADT) of the solid composition V1 was reached at 55 ° C. during storage.
  • composition E1 according to the invention was inconspicuous and stable over the entire storage period of 250 h.
  • the self-accelerating decomposition temperature (SADT) of the solid composition E1 could not be reached.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
EP15771063.3A 2014-09-19 2015-09-18 Festförmige zusammensetzung für die textilbehandlung Active EP3194551B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15771063T PL3194551T3 (pl) 2014-09-19 2015-09-18 Stała kompozycja do traktowania tekstyliów

Applications Claiming Priority (2)

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DE102014218950.0A DE102014218950A1 (de) 2014-09-19 2014-09-19 Festförmige Zusammensetzung für die Textilbehandlung
PCT/EP2015/071442 WO2016042128A1 (de) 2014-09-19 2015-09-18 Festförmige zusammensetzung für die textilbehandlung

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EP3194551B1 true EP3194551B1 (de) 2020-08-12

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US (1) US10479962B2 (pl)
EP (1) EP3194551B1 (pl)
KR (1) KR20170058399A (pl)
DE (1) DE102014218950A1 (pl)
ES (1) ES2821819T3 (pl)
PL (1) PL3194551T3 (pl)
WO (1) WO2016042128A1 (pl)

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PL3828255T3 (pl) * 2019-11-29 2024-03-25 Henkel Ag & Co. Kgaa Wielokomorowy produkt stanowiący środek piorący o dużym kontraście między komorami

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US4116885A (en) 1977-09-23 1978-09-26 The Procter & Gamble Company Anionic surfactant-containing detergent compositions having soil-release properties
CA1190695A (en) 1981-05-14 1985-07-16 George J. Stockburger Anionic textile treating compositions
DE3324258A1 (de) 1982-07-09 1984-01-12 Colgate-Palmolive Co., 10022 New York, N.Y. Nichtionogene waschmittelzusammensetzung mit verbesserter schmutzauswaschbarkeit
ATE73150T1 (de) 1984-12-21 1992-03-15 Procter & Gamble Blockpolyester und aehnliche verbindungen, verwendbar als verschmutzungsentferner in waschmittelzusammensetzungen.
US4711730A (en) 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
US4713194A (en) 1986-04-15 1987-12-15 The Procter & Gamble Company Block polyester and like compounds having branched hydrophilic capping groups useful as soil release agents in detergent compositions
GB8617255D0 (en) 1986-07-15 1986-08-20 Procter & Gamble Ltd Laundry compositions
GB8629936D0 (en) 1986-12-15 1987-01-28 Procter & Gamble Laundry compositions
US4721580A (en) 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
SG76454A1 (en) 1988-08-26 2000-11-21 Procter & Gamble Soil release agents having allyl-derived sulfonated end caps
GB8925285D0 (en) 1989-11-09 1989-12-28 Unilever Plc Bleaching composition
DE4001415A1 (de) 1990-01-19 1991-07-25 Basf Ag Polyester, die nichtionische tenside einkondensiert enthalten, ihre herstellung und ihre verwendung in waschmitteln
DK0737738T3 (da) * 1995-04-12 2003-10-20 Cleantabs As Blegemiddeltablet
EP0872544A1 (en) * 1997-04-14 1998-10-21 The Procter & Gamble Company Dry effervescent granules and granular compositions comprising the same
DE10033827A1 (de) * 2000-07-14 2002-01-31 Henkel Kgaa Kompartiment-Hohlkörper
AU2001287878A1 (en) * 2000-09-20 2002-04-02 Reckitt Benckiser Inc. Improvements in enzyme containing tablets
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PL1903098T3 (pl) 2006-07-27 2009-04-30 Evonik Treibacher Gmbh Powlekane cząstki peroksywęglanu sodowego
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US20170275574A1 (en) 2017-09-28
WO2016042128A1 (de) 2016-03-24
ES2821819T3 (es) 2021-04-27
EP3194551A1 (de) 2017-07-26
PL3194551T3 (pl) 2021-03-08
DE102014218950A1 (de) 2016-03-24
US10479962B2 (en) 2019-11-19
KR20170058399A (ko) 2017-05-26

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