EP3194551A1 - Festförmige zusammensetzung für die textilbehandlung - Google Patents
Festförmige zusammensetzung für die textilbehandlungInfo
- Publication number
- EP3194551A1 EP3194551A1 EP15771063.3A EP15771063A EP3194551A1 EP 3194551 A1 EP3194551 A1 EP 3194551A1 EP 15771063 A EP15771063 A EP 15771063A EP 3194551 A1 EP3194551 A1 EP 3194551A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- weight
- composition according
- compound
- organic
- 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.)
- Granted
Links
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- 229920002959 polymer blend Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 1
- 235000019833 protease Nutrition 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- RYMZZMVNJRMUDD-HGQWONQESA-N simvastatin Chemical compound C([C@H]1[C@@H](C)C=CC2=C[C@H](C)C[C@@H]([C@H]12)OC(=O)C(C)(C)CC)C[C@@H]1C[C@@H](O)CC(=O)O1 RYMZZMVNJRMUDD-HGQWONQESA-N 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical class [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 108010038851 tannase Proteins 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 1
- 108010031354 thermitase Proteins 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 108010068608 xanthan lyase Proteins 0.000 description 1
- 108010083879 xyloglucan endo(1-4)-beta-D-glucanase Proteins 0.000 description 1
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
-
- 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
-
- 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
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 soils such as e.g. Colored fruit and vegetable stains is a central quality feature of a detergent.
- the bleachable dirt is to be bleached and / or removed.
- the textile should not be damaged by bleaching.
- a solid bleach composition which can be used as an additive should contain little additional ingredients in addition to the bleach-active compound for gentle use of the resources.
- a solid bleach additive in a water-soluble casing as a metering unit, it is advantageous if said bleach additive occupies a small volume. The rationalization of additional ingredients and the reduction in the volume of the total composition inevitably lead to a high concentration of bleach-active compound.
- bleach additive which is effective on the textile.
- organic bleach activators are understood by the person skilled in the art to mean chemical compounds which increase the bleaching action in the presence of peroxide compounds.
- organic bleach activators contact an increased concentration of the bleach-active compound resulting in thermal instability.
- the same problem can arise when packaging a bleach additive in a single dose in a portion coated with water-soluble material.
- the water-soluble shell material usually contains organic compounds which also come into contact with the concentrated solid bleach additive.
- a further object of the invention was to provide storage-stable solid compositions having 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 dosing unit for the textile treatment, which comprise a solid-form composition with a high concentration of peroxide compound, which is made up in a water-soluble casing. Upon contact with water, said compositions are released from the portion serving as a dosing 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 part of a textile laundry as an additive.
- compositions of the invention can be used outstandingly as an additive to detergents, in particular liquid detergents, in textile treatment. It is an increase in the washing performance causes.
- a first subject of the invention is therefore a solid composition for use in textile treatment, each containing a total amount of each based on the total weight of the solid composition
- the total amount of the organic compound in the solid composition is 10 to 50% by weight.
- the solid composition may contain, in addition to the mandatory ingredients, other optional ingredients.
- the total amounts are selected from the weight ranges given in such a way that, together with the amounts of the optional ingredients for said solid-form composition based on their total weight, 100 wt .-% result.
- a composition according to the definition of the invention is solid when in the solid state at 25 ° C and 1013 mbar.
- a composition is liquid according to the definition of the invention when in liquid state at 25 ° C and 1013 mbar.
- a chemical compound is an organic compound when the molecule of the chemical compound contains at least one covalent bond between carbon and hydrogen.
- a chemical compound is, inversely to the definition of the organic compound, an inorganic compound when the molecule of the chemical compound does not contain a covalent bond between carbon and hydrogen. This definition applies inter alia to inorganic peroxide compounds as a chemical compound mutatis mutandis.
- a peroxide compound is a chemical compound containing, as a structural fragment, the peroxo atomic group -O-O-.
- weight-average molar masses M w which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expedient against an external standard he follows.
- the solid composition according to the invention is formed from a plurality of solid particles.
- Such an embodiment of the solid composition is preferably present as a powder or granules.
- the said solid particles in turn preferably have a particle diameter Xso, 3 (volume average) in a range of 100 to 1500 ⁇ .
- Xso, 3 volume average
- These particle sizes can be determined by sieving or by means of a particle size analyzer Camsizer from Retsch.
- the solid composition according to the invention necessarily contains a defined amount of peroxide compound. It has proved to be preferred according to the invention if the solid-form composition according to the invention, based on the total weight of the composition, contains peroxide compounds in a total amount of from 20 to 50% by weight, in particular from 25 to 45% by weight. It is preferred according to the invention if 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 peroxyacids or mixtures of at least two of these compounds. It is particularly preferred according to the invention if the peroxide compound is selected from sodium percarbonate, sodium perborate, Natnumperoxodisulfat or mixtures thereof. Sodium percarbonate is a most preferred peroxide compound. Sodium percarbonate is an addition compound of hydrogen peroxide to sodium carbonate with the formula y Na2C03 X H2O2, where x is the molar amount of hydrogen peroxide per mole of Na2CÜ3. Most preferably, the peroxide compound is Na 2 CO 3 - 1.5 hhC 1 having 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% (measured in each case by titration with potassium permanganate).
- the peroxide compound is particulate, in particular as a powder or granules.
- the particles containing the peroxide compound for example the powder or granules
- the particles containing the peroxide compound have a bulk density of 0.70 to 1.30 kg / dm 3 , more preferably with a bulk density of 0.85 to 1.20 kg / dm 3 (eg in each case measured according to ISO 697) have.
- peroxide compounds whose particles have an average particle size (volume average) Xso, 3 of 0.40 to 0.95 mm, in particular 0.50 to 0.90 mm, are preferred (eg measured with sieve analysis or by a particle size analyzer) Camsizer, retsch company).
- a solid peroxide compound, in particular sodium percarbonate can be provided with a coating for additional protection against decomposition on the surface.
- the coating should protect against decomposition of the percarbonate.
- Suitable coating agents are preferably water-soluble passivating agents, such as, for example, sodium bicarbonate, sodium carbonate, sodium sulfate or metaborate compounds. It may be preferred according to the invention if the solid peroxide compound, in particular sodium percarbonate, is coated on the surface with at least sodium sulfate.
- the solid-like Peroxidvervindung an average particle size Xso, 3 from 0.40 to 0.95 mm, in particular from 0.50 to 0.90 mm has (eg measured with sieve analysis or by a particle size analyzer Camsizer, company Retsch) and are coated with sodium sulfate.
- Sodium percarbonate particles with sodium bicarbonate coating obtainable by a surface reaction and their preparation in a fluidized bed reactor are known to the person skilled in the art from document EP 1 227 063 A2.
- said sodium bicarbonate coatings are not desirable in the production due to further technical process steps with energy input.
- the phlegmatization ie reduction or prevention of possible heat formation by an exothermic decomposition of the solid peroxide compound
- the peroxide compound used with a phlegmatizer in particular with a metaborate compound
- the peroxide compound content is from 50 to 100% by weight of Metaborate coated peroxide compound.
- the phlegmatizing coating of the solid peroxide compound is not mandatory.
- composition of the invention necessarily contains a total amount of 10 to 20 wt .-% of one or more organic bleach activators. It is preferred if the compositions according to the invention contain a total amount of from 1 to 18% by weight, particularly preferably from 12 to 16% by weight, again preferably from 10 to 15% by weight, very particularly preferably from 1 to 14 Wt .-%, contains.
- Preferred organic bleach activators are compounds which, under perhydrolysis conditions, give peroxycarboxylic acids (in particular aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms), and / or optionally substituted perbenzoic acid.
- peroxycarboxylic acids in particular aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms
- perbenzoic acid in particular aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms
- Perhydrolysis is known to the person skilled in the art as a reaction in which, in a protic solvent (eg water), an anion ⁇ - ⁇ - ⁇ covalently binds to a reactant RX by nucleophilic substitution to give the compound ROOH and the cleavage of a leaving group X leads to lysis of the compound chemical bond between R and X causes.
- a protic solvent eg water
- compositions containing organic bleach activator of at least one compound of the group of compounds which form aliphatic peroxycarboxylic acids under perhydrolysis conditions are preferred according to the invention. It is particularly preferred if the organic bleach activator is selected from at least one compound of the poly-N-acylated organic amines. The aforementioned total amounts apply mutatis mutandis for these special organic bleach activators.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulphonates, especially n -Nonanoyl or Isononanloxybenzolsulfonat (n- or iso-NOBS) is particularly preferably used.
- TAED tetraacetylethylenediamine
- DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
- TAGU acylated glycolurils
- composition according to the invention contains
- the inventive composition of the first subject of the invention necessarily contains a defined amount of bicarbonate, calculated as sodium bicarbonate.
- Hydrogen carbonate is to be understood according to the invention as meaning a chemical compound which contains at least one hydrogencarbonate ion (HCO3) prior to the preparation of the composition according to the invention and which is different from peroxide compounds according to the invention.
- the amount by weight of bicarbonate in the composition of the present invention is expressed by the definition of the equivalent amount by weight of sodium bicarbonate.
- compositions containing, based on the total weight of the composition, bicarbonate in a total amount of from 7.5 to 30% by weight, calculated as sodium bicarbonate, are preferred according to the invention.
- bicarbonate from sodium bicarbonate, potassium bicarbonate or mixtures thereof.
- the bicarbonate of sodium bicarbonate is suitable.
- the bicarbonate-containing particles (for example the powder or granules) have a bulk density of 0.40 to 1, 50 kg / dm 3 , particularly preferably having a bulk density of 0.90 to 1, 10 kg / dm 3 ( eg measured in each case according to ISO 697).
- the particles containing the peroxide compound (for example the powder or granules) have a bulk density of 0.70 to 1.30 kg / dm 3 , particularly preferably with a bulk density of 0, 85 to 1, 20 kg / dm 3 (eg, in each case measured according to ISO 697) have.
- a very particularly preferred embodiment (A) of the solid-form composition according to the invention for use in textile treatment, in each case based on the total weight of the solid composition, contains a total amount of
- particulate hydrogencarbonate calculated as sodium hydrogencarbonate, in particular sodium bicarbonate
- composition of the invention necessarily contains a defined amount by weight of organic compound. It is particularly preferred according to the invention if the composition according to the invention contains, based on its total weight, organic compounds in a total amount of from 20.0% by weight to 35.0% by weight.
- the technical effect is particularly pronounced according to the invention if 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 covalently binds, which is different from carbon and hydrogen.
- the compositions of the invention preferably contain at least one organic grayness inhibitor.
- a graying inhibitor is a chemical compound which prevents or restricts the re-deposition of the soil dispersed in the wash liquor to the fabric.
- the graying inhibitor is preferably present in the composition according to the invention in a total amount of from 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. %, in each case based on the weight of said composition.
- compositions according to the invention contain as an organic grayness inhibitor a polymeric compound which carries at least two anionic groups.
- Preferred anionic groups are selected from carboxylate, sulfonate, sulfate or mixtures thereof.
- the composition according to the invention contains, as an organic compound, at least one graying-inhibiting polysaccharide.
- the liquid washing or cleaning agent preferably contains methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose (CMC), an ether sulfonic acid salt of starch, an ether sulfonic acid salt of cellulose, an acid sulfuric ester salt of cellulose, an acid sulfuric acid ester salt of Starch or a mixture of at least two of these graying-inhibiting polysaccharides.
- CMC carboxymethylcellulose
- an ether sulfonic acid salt of starch an ether sulfonic acid salt of cellulose, an acid sulfuric ester salt of cellulose, an acid sulfuric acid ester salt of Starch or a mixture of at least two of these graying-inhibiting polysaccharides.
- graying-inhibiting polysaccharide carboxymethylcellulose, in particular sodium carboxymethylcellulose, in the composition
- the preferred total amount of graying-inhibiting polysaccharide, in particular of carboxymethylcellulose, is from 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. %, in each case based on the weight of said composition.
- the composition according to the invention contains at least one soil-release active substance as organic compound.
- Soil release agents are often referred to as “soil release” agents or because of their ability to render the treated surface, for example, the fiber, dirt repellent, "soil repellents". Because of their chemical similarity to polyester fibers particularly effective soil release agents, but can also show the desired effect in fabrics of other materials are copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-releasing polyesters of the type mentioned as well as their use in detergents have been known for a long time.
- European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
- European Patent EP 185 427 methyl or ethyl end-capped polyester with ethylene and / or propylene terephthalate and Polyethylene oxide terephthalate units and detergents containing such soil release polymer known.
- European Patent EP 241 984 relates to a polyester which, besides oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units. From the European patent EP 241 985 polyesters are known which in addition to oxy- ethylene groups and terephthalic acid units 1, 2-propylene, 1, 2-butylene and / or 3-methoxy-1, 2-propylene groups and glycerol units and with Ci- to C4-alkyl groups are end-group-capped.
- European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 from ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 to 0.95.
- European Patent Application EP 272 033 discloses, at least in part, polyesters having poly-propylene terephthalate and polyoxyethylene terephthalate units which are end-capped by ⁇ -4-alkyl or acyl radicals.
- European Patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European patent application EP 357,280, sulfonation of unsaturated end groups produces soil release polyesters with terephthalate, alkylene glycol and poly-C 2-4 glycol units.
- the composition according to the invention contains as organic compound at least one soil release-capable polyester comprising the structural units I to III or I to IV,
- d, e and f independently of one another each represent a number from 1 to 50
- g is a number from 0 to 5
- Ph is a 1,4-phenylene radical
- sPh is a 1, 3-phenylene radical substituted in position 5 by a group -SO3M
- M is Li, Na, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or tetraalkylammonium, wherein the alkyl radicals of the ammonium ions are C 1 -C 22 -alkyl- or C2-Cio-hydroxyalkyl radicals or any mixtures thereof,
- R 1 , R 3 , R 4 , R 5 and R 6 independently of one another each represent hydrogen or a C 1 -C 18 -n- or iso-alkyl group
- R 7 stands for a linear or branched C 1 -C 30 -alkyl group or for a linear or branched C 2 -C 30 -alkenyl group, for a cycloalkyl group with 5 to 9 carbon atoms, for a C 6 -C 30 -aryl group or for a C 6 -C 30 -arylalkyl group, and
- Polyfunctional unit for a unit having 3 to 6 functional groups capable of esterification reaction for a unit having 3 to 6 functional groups capable of esterification reaction.
- Such polyesters can be obtained, for example, by polycondensation of terephthalic acid dialkyl ester, 5-sulfoisophthalic acid dialkyl ester, alkylene glycols, optionally polyalkylene glycols (at a, b and / or c> 1) and polyalkylene glycols end capped on one side (corresponding to unit III). It should be pointed out that for numbers a, b, c> 1 there is a polymeric skeleton and thus the coefficients as an average can assume any value in the given interval. This value reflects the number average molecular weight.
- polyethylene glycol-co-propylene glycol having number-average molecular weights of 100 to 2000 g / mol.
- from 1 to 50 units (I) can be contained per polymer chain.
- unit (II) is an ester of 5-sulfoisophthalic acid with one or more difunctional, aliphatic alcohols in question, preferably used are the aforementioned. In the structures, for example, 1 to 50 units (II) may be present.
- Citric acid malic acid, tartaric acid and gallic acid, particularly preferably 2, 2-dihydroxymethyl-propionic acid, may be used as examples for this purpose.
- polyhydric alcohols such as pentaerythrol, glycerol, sorbitol and / or trimethylolpropane can be used.
- These may 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 ( Trimesithklare) act.
- the proportion by weight of crosslinking monomers, based on the total weight of the polyester, can be, for example, up to 10% by weight, in particular up to 5% by weight and more preferably up to 3% by weight.
- 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, wherein the number average molecular weight can be determined by size exclusion chromatography in aqueous solution using a calibration using narrowly distributed polyacrylic acid Na salt standards.
- the number-average molecular weights are preferably in the range from 800 to 25,000 g / mol, in particular from 1,000 to 15,000 gmol, particularly preferably from 1,200 to 12,000 g / mol.
- solid polyesters which have softening points above 40 ° C. are preferably used as part of the particle of the second type; they preferably have a softening point between 50 and 200 ° C, more preferably between 80 ° C and 150 ° C, and most preferably between 100 ° C and 120 ° C.
- the synthesis of the polyesters can be carried out by known methods, for example by first heating the abovementioned components with addition of a catalyst at normal pressure and then building up the required molecular weights in vacuo by distilling off superstoichiometric amounts of the glycols used.
- Suitable for the reaction are the known transesterification and condensation catalysts, such as, for example, titanium tetraisopropylate, dibutyltin oxide, alkali metal or alkaline earth metal alcoholates or antimony trioxide / calcium acetate.
- Preferred polyesters are of solid consistency and can easily be ground into powder or compacted or agglomerated into granules of defined particle sizes.
- the granulation can be carried out in such a way that the resulting as a melt in the synthesis Copolymers are solidified by cooling in a cool gas stream, such as air or nitrogen, or by applying to a flaking roll or on a treadmill to flakes or scales.
- This coarse material can optionally be further ground, for example, in the roll mill or in the screen mill, which can be followed by a sieving and a rounding as described above.
- the granulation can also be carried out in such a way that the polyesters are ground to powder after solidification and then reacted by compaction or agglomeration and the above-described rounding into granules with defined particle sizes.
- the composition according to the invention contains at least one enzyme as organic compound.
- all enzymes established in the state of the art for textile treatment can be used in this regard.
- it is one or more enzymes which 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 and / or lipases and mixtures thereof are particularly preferred, and proteases are particularly preferred.
- These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
- subtilisin type those of the subtilisin type are preferable.
- 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 enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
- Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark.
- the subtilisins 147 and 309 are sold under the trade name Esperase®, or Savinase® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP® protease variants derived. Further useful proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Genencor, sold under the trade name Protosol® by Advanced Biochemicals Ltd.
- amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and their further developments improved for use in detergents or cleaners.
- the B. licheniformis enzyme is available from Novozymes under the name Termamyl® and from Genencor under the name Purasta DST. Further development products of this ⁇ -amylase are available from Novozymes under the trade name Duramyl® and Termamy Dultra, from Genencor under the name Purasta DOxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. B.
- amyloliquefaciens ⁇ -amylase is sold by Novozymes under the name BAN®, and variants derived from B. stearothermophilus ⁇ -amylase under the names BSG® and Novamyl®, also from Novozymes. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the further developments of the a-amylase from Aspergillus niger and A.
- oryzae available under the trade name Fungamyl® from the company Novozymes are suitable.
- Further advantageously usable commercial products are, for example, the Amylase-LT®, as well as Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter also from the company Novozymes.
- variants of these enzymes obtainable by point mutations can be used according to the invention.
- lipases or cutinases which can be used according to the invention, which are contained in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors, are the lipases which are originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold for example by the company Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
- Lipases which are likewise useful are sold by 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®.
- Lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
- Lipase® and Lipomax® are preparations M1 Lipase® and Lipomax®, originally sold by Gist-Brocades, and those manufactured by Meito Sangyo KK, Japan, under the name Lipase MY-30®, Lipase OF® and Lipase PL® marketed enzymes, also the product Lumafast® from Genencor.
- cellulases may be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement each other in terms of their various performance aspects.
- These performance aspects include in particular the contributions of the cellulase to the primary washing performance of the composition (cleaning performance), to the secondary washing performance of the composition (anti-redeposition effect or graying inhibition), to softening (tissue effect) or to the exercise of a "stone-washed" effect.
- cleaning performance cleaning performance
- anti-redeposition effect or graying inhibition anti-redeposition effect or graying inhibition
- tissue effect tissue effect
- a useful fungal, endoglucanase (EC ) -rich cellulase preparation or its further developments is offered by the company Novozymes under the trade name Celluzyme®
- the products Endolase® and Carezyme® likewise available from the company Novozymes are based on the 50 kD-EG or the 43 kD-EG H.
- insolens DSM 1800 Other commercially available products of this company are Cellusoft®, Renozyme® and Celluclean.RTM .. Also usable are, for example, the 20 kD-EG from Melanocarpus, those from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch® Other commercial products of AB Enzymes are Econa se® and Ecopulp®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax® is available. Further commercial products of Genencor are "Genencor detergent cellulase L" and lndiAge®Neutra.
- variants of these enzymes obtainable by point mutations can be used according to the invention.
- Particularly preferred 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 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 names Mannaway® by the company Novozymes or Purabrite® by the company Genencor.
- pectin-destroying enzymes in the context of the present invention are also counted enzymes with the designations pectinase, pectate lyase, pectin esterase, pectin methoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectin esterase, pectin-pectin hydrolase, pectin-polymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin-polygalacturonase, Endo-polygalacturonase, poly-a-1, 4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1, 4-a-galacturonidase, exopolygalacturonase, poly (galacturonate) Hydrolase, exo-
- enzymes suitable for this purpose are, for example, under the name Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes, and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
- compositions according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 8 to 5 percent by weight, based on active protein.
- the enzymes are in a total amount of 0.001 to 4 wt .-%, more preferably from 0.01 to 3 wt .-%, even more preferably from 0.05 to 1, 25 wt .-% and particularly preferably from 0, 2 to 1, 0 wt .-% in these agents.
- organic compounds organic surfactants, organic builders, organic complexing agents, organic optical brighteners, organic pH regulators, perfume, organic dye, organic dye transfer inhibitor or mixtures thereof may be included in the composition of the invention.
- the composition of the invention should preferably be used as an additive in the context of a textile laundry.
- the composition according to the invention 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. , Containing surfactant.
- composition according to the invention contains surfactant as an organic compound, it is preferable to use soap as the surfactant.
- soap are the water-soluble sodium or potassium salts of the saturated and unsaturated fatty acids having from 10 to 20 carbon atoms, the rosin acids of rosin (yellow rosin soaps) and naphthenic acids which are used as solid or semi-solid mixtures mainly for washing and cleaning purposes.
- Sodium or potassium salts of the saturated and unsaturated fatty acids having 10 to 20 carbon atoms, in particular having 12 to 18 carbon atoms, are preferred soaps according to the invention.
- compositions according to the invention are characterized in that they contain, based on their weight, from 0.1 to 4.0% by weight, particularly preferably from 0.5 to 3.5% by weight, very particularly preferably from 1.0 to 3.0 wt .-% soap (s) included. It is preferred according to the invention if the solid compositions according to the invention contain no nonionic surfactant.
- Organic builders which may be present in the composition according to the invention are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids 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 polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
- polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.
- Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
- An organic optical brightener is preferably selected from the substance classes of distyrylbiphenyls, the stilbenes, the diamino-2,2-stilbenedisulfonic acids 4.4, the coumarins, the dihydroquinolinones, the 1, 3-diaryl pyrazolines, naphthalimides of the benzoxazole systems , the benzisoxazole systems, the benzimidazole systems, the heterocyclic substituted pyrene derivatives 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'-disulphonic acid (available, for example, as Tinopal® UNPA from BASF SE), hexasodium 2,2'- [vinylene bis [(3-sulphonato-4,1-phenylene ) imino [6- (diethylamino) -1, 3,5-triazine-4,2-diyl] imino]
- Suitable color transfer inhibiting polymers include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole and mixtures thereof. Particular preference is given to using polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) as color transfer inhibitor.
- 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.
- PVP / PVI copolymer 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, under the name Sokalan® HP 66 from BASF are.
- composition according to the invention contains at least the following organic compounds, based on the weight of the composition:
- inventive composition contains a total amount of 12.7 wt .-% to 50.0 wt .-%, in particular 20.0 wt .-% to 35.0 wt .-%, of organic compounds.
- composition according to the invention contains at least the following organic compounds, based on the weight of the composition:
- a, b and c independently of one another each represent a number from 1 to 200
- d, e and f independently of one another each represent a number from 1 to 50
- g is a number from 0 to 5
- Ph is a 1,4-phenylene radical
- sPh is a 1, 3-phenylene radical substituted in position 5 with a group -SO3M
- M is Li, Na, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or Tetraalkylammonium, where the alkyl radicals of the ammonium ions are C 1 -C 22 -alkyl or C 2 -C 10 -hydroxyalkyl radicals or any desired mixtures thereof,
- R, R 2 , R 3 , R 4 , R 5 and R 6 independently of one another each represent hydrogen or a C 1 -C 18 -n- or iso-alkyl group
- R 7 is a linear or branched C 1 -C 30 -alkyl group or a linear or branched C 2 -C 30 -alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, a C 6 -C 30 -aryl group or a C 6 -C 30 -arylalkyl group, and
- Polyfunctional unit for a unit having 3 to 6 functional groups capable of esterification reaction
- composition according to the invention contains a total amount of 12.8 wt .-% to 50.0 wt .-%, in particular 20.0 wt .-% to 35.0 wt .-%, of organic compounds.
- the solid composition according to the invention based on the total weight, of solid, basic silicate (calculated as water glass), in a total amount of at most 20.0 wt .-%, in particular of at most 15.0 wt .-%, contains. Most preferably, the composition according to the invention is free of solid, basic silicate.
- the solid composition according to the invention is prepared by mixing the raw materials.
- a batch process or a continuous mixing process can be used. It is preferred in accordance with the invention to employ those mixing processes in which the particles of the ingredients (e.g., the powder or granules) are not mechanically disrupted.
- Suitable mixers are especially tumble mixers, paddle mixers (Forberg, Fa. Lödige, Fa. Gericke) or Helix mixers (Fa. Amixon, Fa. Gebrueder Ruberg).
- the ingredients of the solid composition according to the invention are mixed with low energy input, in particular mixing tools are used, which mix with 0.1 to 5 m / s peripheral speed.
- the solid-like composition of the first article is outstandingly suitable for packaging in a water-soluble portion.
- the solid-state composition according to the invention of the first subject of the invention is in a chamber formed of water-soluble material.
- the water-soluble material forms walls of the chamber and thereby envelops the inventive composition of the first subject of the invention.
- a second subject of the invention is therefore a portion for use in textile treatment, comprising at least one chamber with walls of water-soluble material, wherein in this at least one chamber, a composition of the first subject of the invention is included.
- a chamber is a space bounded by walls (e.g., by a foil), which may exist even without the material to be dosed (possibly changing its shape). A layer of a surface coating thus does not explicitly fall under the definition of a wall.
- the walls of the chamber are made of a water-soluble material.
- the water solubility of the material can be determined with the aid of a square film of 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 heated to 20 ° C in a 1 liter beaker with a circular bottom surface (Schott, Mainz, 1000 mL beaker, low mold) so that the surface of the clamped film is at right angles to the Bottom surface of the beaker is arranged, the upper edge of the frame is 1 cm below the water surface and the lower edge of the frame parallel to the bottom surface of the Beaker is aligned such that the lower edge of the frame along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is located above the center of the radius of the beaker bottom.
- the material should dissolve with stirring (stirring speed magnetic stirrer 300 rpm, stirring bar: 6.8 cm long, diameter 10 mm) within 600 seconds in such a way that with the naked eye, no single solid-shaped film particles are more visible.
- the walls are preferably made of a water-soluble film.
- This film may according to the invention preferably have a thickness of at most 150 ⁇ (more preferably of at most 120 ⁇ ).
- Preferred walls are therefore made of a water-soluble film and have a thickness of at most 150 ⁇ (more preferably of at most 120 ⁇ , most preferably of at most 90 ⁇ ) on.
- the portion preferably contains the composition of the first subject of the invention in a total amount of 4.0 to 10.0 g, in particular from 5.0 to 9.0 g.
- composition of the first subject of the invention is used as an additive to a detergent, in particular a liquid detergent
- a detergent in particular a liquid detergent
- the composition of the first article is provided in a water-soluble portion for use in textile treatment, comprising at least two chambers with walls of water-soluble material, characterized in that a) at least one of said chambers contains a first composition, said first composition containing at least one surfactant, and b) at least one further of said chambers containing a second composition, said second composition being a composition of the first subject of the invention.
- the first composition is liquid.
- the surfactant of the first composition both anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants can be used. 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.
- the anionic surfactant used may preferably be sulfonates and / or sulfates.
- the content of anionic surfactant is 5 to 25 wt .-% and preferably 8 to 20 wt .-%, each based on the entire first or second liquid low-water detergent or cleaning agent.
- Preferred surfactants of the sulfonate type are C9-i3-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C12 -18 monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis the sulfonation obtained.
- esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters secondary Alcohols of these chain lengths are preferred.
- the Ci2-Ci6-alkyl sulfates and Ci2-Ci5-alkyl sulfates and Cw-cis-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 C7-2i alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-11 alcohols having on average 3.5 moles of ethylene oxide (EO) or C12-alcohols. Fatty alcohols with 1 to 4 EO are suitable.
- Suitable anionic surfactants are soaps.
- Suitable are 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.
- the anionic surfactants and the soaps may be in the form of their sodium, potassium or magnesium or ammonium salts.
- the anionic surfactants are 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 comprises a monoethanolamine-neutralized alkylbenzenesulfonic acid, especially C9-i3-alkylbenzenesulfonic acid, and / or a monoethanolamine-neutralized fatty acid.
- 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 are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred.
- Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 4 EO or 7 EO, n-alcohol with 7 EO, C 3 i5-alcohols containing 5 EO, 7 EO or 8 EO, C 12 18-alcohols with 5 EO or 7 EO and mixtures of these.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
- NRE narrow rank ethoxylates
- fatty alcohols with more than 12 EO can also be used.
- Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a Ci6 -18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO.
- the first composition contains a C 12-18 fatty alcohol with 7 EO, a Ci3-is-oxoalcohol with 7 EO and / or a Ci3-is-oxoalcohol with 8 EO as nonionic surfactant.
- the content of nonionic surfactant is 1 to 25 wt .-%, and preferably 2 to 20 wt .-%, each based on the entire first composition.
- the total amount of surfactant in the first composition is preferably up to 85% by weight, preferably 40 to 75% by weight and more preferably 50 to 70% by weight, based in each case on the entire first composition.
- the first composition additionally contains at least one polyalkoxylated polyamine.
- the polyalkoxylated polyamine is a polymer having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms.
- the polyamine has at the ends (terminus and / or side chains) primary amino functions and internally preferably both secondary and tertiary amino functions; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine.
- the ratio of primary to secondary amino groups in the polyamine is preferably in the range of 1: 0.5 to 1: 1, 5, in particular in the range of 1: 0.7 to 1: 1.
- the ratio of primary to tertiary amino groups in the polyamine is preferably in the range of 1: 0.2 to 1: 1, in particular in the range of 1: 0.5 to 1: 0.8.
- the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol.
- the N atoms in the polyamine are separated from one another by alkylene groups, preferably by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number.
- ethylene groups 1, 2-propylene groups, 1, 3-propylene groups, and mixtures thereof.
- Polyamines bearing ethylene groups as said alkylene group are also referred to as polyethyleneimine or PEI.
- PEI is an inventively particularly preferred polymer with N-atom-containing backbone.
- the primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function must be alkoxy-substituted.
- the average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably from 1 to 100, in particular from 5 to 50.
- the alkoxy groups in the polyalkoxylated polyamine are preferably polypropoxy groups which are bonded directly to N atoms, and / or Polyethoxy groups which are attached to any existing propoxy and N atoms which do not carry propoxy groups.
- Polyethoxylated polyamines are obtained by reacting polyamines with ethylene oxide (EO for short).
- EO ethylene oxide
- the polyalkoxylated polyamines containing ethoxy and propoxy groups are preferably accessible by reaction of polyamines with propylene oxide (abbreviated to PO) and subsequent reaction 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, especially 15 to 30.
- the terminal OH function polyalkoxy substituents in the polyalkoxylated polyamine may be partially or completely etherified with an O-C10, in particular C1-C3-alkyl group.
- Polyalkoxylated polyamines which are particularly preferred according to the invention can be selected from polyamine reacted with 45EO per primary and secondary amino function, PEI's reacted with 43EO per primary and secondary amino function, PEI's reacted with 15EO + 5PO per primary and secondary amino function, PEI's 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 secondary amino function and PEI's reacted with 15PO + 5EO per primary and secondary amino function.
- a most preferred alkoxylated polyamine is PEI containing 10 to 20 nitrogen atoms reacted with 20 units of EO per primary or secondary amino function of the polyamine.
- a further preferred subject of the invention is the use of polyalkoxylated polyamines which are obtainable by reacting polyamines with ethylene oxide and optionally additionally propylene oxide. If polyalkyoxylated polyamines are used with ethylene oxide and propylene oxide, the proportion of propylene oxide in the total amount of the alkylene oxide is preferably 2 mol% to 18 mol%, in particular 8 mol% to 15 mol%.
- the first composition based on the total weight thereof, preferably contains polyalkoxylated polyamines in a total amount of from 0.5 to 10% by weight, in particular from 1.0 to 7.5% by weight.
- the first composition formulated in the water-soluble portion in the first chamber may contain water, wherein, especially for liquid first compositions, the content of water based on the entire first composition is at most 20% by weight, preferably at most 15% by weight, is.
- the water content is determined by Karl Fischer method.
- the first composition may contain other ingredients that further enhance the performance and / or aesthetics 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, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, anti-shrinkage agents, anti-crease agents , antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, skin-care active ingredients, swelling and anti-slip agents, softening components and UV absorbers.
- the portion comprises mandatory 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 portions can be prepared by either vertical fill seal (VFFS) or thermoforming techniques.
- the thermoforming process generally includes forming a first layer of water-soluble film material to form at least one protrusion for receiving at least one composition therein, filling the composition into the respective protrusion, covering the composition-filled protrusions with a second layer of water-soluble one Film material and sealing the first and second layers together at least around the protrusions.
- 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 blends.
- the wrapper may be formed of one or two or more layers of the water-soluble film material.
- the water-soluble film material of the first layer and the further layers, if present, may be the same or different. It is preferable that 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 whose molecular weight is in each case in the range of 10,000 to 1,000,000 gmol _ , preferably from 20,000 to 500,000 gmol ⁇ more preferably from 30,000 to 100,000 gmol "1 and especially from 40,000 to 80,000 gmol 1 is located.
- polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
- polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble material comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
- the film material suitable as water-soluble material may additionally be added polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers.
- 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, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
- Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
- Suitable water-soluble films for use as the water-soluble material of the water-soluble potion according to the invention are films sold under the name Monosol M8630 by MonoSol LLC.
- Other suitable films include films named Solublon® PT, Solublon® KA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
- the portion preferably contains the second composition in a total amount of from 4.0 to 10.0 g, in particular from 5.0 to 9.0 g.
- a third subject of the invention is the use of a composition of the first subject of the invention for textile treatment.
- the composition is packaged in a water-soluble portion of the second subject of the invention.
- the embodiment of a water-soluble portion with at least two chambers is preferred, as described in the context of the second subject of the invention.
- a fourth subject of the invention is a textile treatment process comprising the steps of dosing a composition of the first subject of the invention to produce an aqueous wash liquor and contacting the resulting wash liquor with fabrics.
- a solid composition for use in textile treatment containing in each case based on the total weight of the solid composition in each case a total amount of
- the total amount of organic compound in the solid composition is 10 to 50% by weight, preferably 20 to 35% by weight.
- composition according to item 1 characterized in that based on the total weight of the composition peroxide compound in a total amount of 32 to 55 wt .-%, in particular from 33 to 45 wt .-%, are included.
- composition according to one of the items 1 or 2 characterized in that the peroxide compound is selected from sodium percarbonate, sodium perborate, sodium peroxodisulfate or mixtures thereof.
- composition according to one of the items 1 to 6 characterized in that the organic bleach activator is selected from at least one compound of the group of compounds which form aliphatic peroxycarboxylic acids under perhydrolysis conditions.
- Composition according to one of the items 1 to 7 characterized in that the organic bleach activator is selected from at least one compound of the poly-N-acylated organic amines.
- Composition according to one of the items 1 to 8 characterized in that based on the total weight of the composition bicarbonate in a total amount of 7.5 to 30 wt .-%, calculated as sodium bicarbonate, is included.
- Composition according to one of the items 1 to 9 characterized in that bicarbonate is selected from sodium bicarbonate, potassium bicarbonate or mixtures thereof.
- composition according to one of the items 1 to 10 characterized in that bicarbonate is sodium bicarbonate.
- Composition according to one of the items 1 to 13 characterized in that based on the total weight of the composition as an organic compound organic bleach activator in a total amount of 5 to 20 wt .-%, in particular 10 to 15 wt .-%, is included.
- Portion for use in textile treatment comprising at least two chambers with walls of water-soluble material, characterized in that a) at least one of these chambers contains a first composition, said first composition containing at least one surfactant, and b) at least one further of these chambers contains a second composition, this second composition being a composition according to any one of items 1 to 14.
- Portion according to one of the items 15 or 16 characterized in that the first composition contains at least one anionic surfactant and at least one nonionic surfactant.
- the water-soluble material contains at least one water-soluble polymer.
- a textile treatment process comprising the steps of dosing a composition according to any one of items 1 to 14 to produce an aqueous wash liquor and contacting the resulting wash liquor with fabrics. Examples
- the sodium percarbonate granules were homogeneously coated with 6 g of sodium sulfate by a known method (WO 2008/012181 A1) and placed in a tumble mixer. Instead of this coated sodium percarbonate, 53.3% by weight of sodium percarbonate Q35 (containing 88, 18% by weight of sodium percarbonate, Evonik) can be initially charged. The remaining components were added to the tumble mixer and the compositions prepared by dry blending the components for 3 minutes at 10 revolutions / minute.
- a portion of the invention P1 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 non-inventive portion P2 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 film M8630 Fa. Monosol (90 ⁇ ) was clamped on a heatable mold with Doppelkavtician. The stretched film was heated at 105 ° C for a period of 2400 ms and then pulled into the cavity by a vacuum. Subsequently, an appropriate amount of the solid composition of Table 1 was pre-weighed into the first cavity and then the amount of liquid composition L1 of Table 2 was added by syringe into the second cavity. Thereafter, a top film (M8630, 90 ⁇ ) is placed to seal the cavities and heat-sealed (150 ° C, 1000 ms) with the first film. After breaking the vacuum, the portion of the cavity was removed. A wall of the portion's powder chamber was subsequently 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 was filled in a Dewar with temperature probe, the sample tempered at 55 ° C in a warming cabinet and stored. It was measured over a storage period of 250 h at 55 ° C, the temperature of the solid composition in the Dewar flask and plotted against the storage time.
- the non-inventive solid composition V1 showed a strong self-decomposition, in which the sample heated to more than 61 ° C within 100 h and after 140 h to 189 ° C.
- the self-accelerating decomposition temperature (SADT) of the solid composition V1 was reached when stored at 55 ° C.
- Composition E1 according to the invention was inconspicuous and stable over the entire storage period of 250 hours. No self-accelerating decomposition temperature (SADT) of the solid composition E1 could be achieved.
- SADT self-accelerating decomposition temperature
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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)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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PL15771063T PL3194551T3 (pl) | 2014-09-19 | 2015-09-18 | Stała kompozycja do traktowania tekstyliów |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
Publications (2)
Publication Number | Publication Date |
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EP3194551A1 true EP3194551A1 (de) | 2017-07-26 |
EP3194551B1 EP3194551B1 (de) | 2020-08-12 |
Family
ID=54199640
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP15771063.3A Active EP3194551B1 (de) | 2014-09-19 | 2015-09-18 | Festförmige zusammensetzung für die textilbehandlung |
Country Status (7)
Country | Link |
---|---|
US (1) | US10479962B2 (de) |
EP (1) | EP3194551B1 (de) |
KR (1) | KR20170058399A (de) |
DE (1) | DE102014218950A1 (de) |
ES (1) | ES2821819T3 (de) |
PL (1) | PL3194551T3 (de) |
WO (1) | WO2016042128A1 (de) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
EP0185427B1 (de) | 1984-12-21 | 1992-03-04 | The Procter & Gamble Company | Blockpolyester und ähnliche 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 |
EP0357280B1 (de) | 1988-08-26 | 1996-02-28 | The Procter & Gamble Company | Schmutzabweisende Mittel mit von Allylgruppen abgeleiteten sulphonierten Endgruppen |
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 |
EP0737738B1 (de) * | 1995-04-12 | 2003-06-25 | Cleantabs A/S | Bleichmitteltabletten |
EP0872544A1 (de) * | 1997-04-14 | 1998-10-21 | The Procter & Gamble Company | Trockene Brausegranulate und dessen Verwendung in granulierten Zusammensetzungen |
DE10066035B4 (de) * | 2000-07-14 | 2006-06-08 | Henkel Kgaa | Kompartiment-Hohlkörper |
ATE317000T1 (de) * | 2000-09-20 | 2006-02-15 | Reckitt Benckiser Inc | Verbesserungen in enzyme enthaltende tabletten |
FI109685B (fi) | 2001-01-26 | 2002-09-30 | Kemira Chemicals Oy | Menetelmä parantuneen stabiliteetin omaavien natriumperkarbonaattirakeiden valmistamiseksi |
DE102005025660B4 (de) * | 2005-06-03 | 2015-10-15 | Cosma Engineering Europe Ag | Vorrichtung und Verfahren zum Explosionsumformen |
DE502006001853D1 (de) | 2006-07-27 | 2008-11-27 | Evonik Degussa Gmbh | Umhüllte Natriumpercarbonatpartikel |
EP2527421A1 (de) | 2011-05-23 | 2012-11-28 | The Procter & Gamble Company | Wasserlöslicher Dosiereinheitbeutel mit Chelant |
DE102012215107A1 (de) * | 2012-08-24 | 2014-02-27 | Basf Se | Festes Geschirrspülmittel mit verbesserter Proteaseleistung |
-
2014
- 2014-09-19 DE DE102014218950.0A patent/DE102014218950A1/de not_active Withdrawn
-
2015
- 2015-09-18 US US15/512,298 patent/US10479962B2/en not_active Expired - Fee Related
- 2015-09-18 EP EP15771063.3A patent/EP3194551B1/de active Active
- 2015-09-18 ES ES15771063T patent/ES2821819T3/es active Active
- 2015-09-18 KR KR1020177010176A patent/KR20170058399A/ko unknown
- 2015-09-18 WO PCT/EP2015/071442 patent/WO2016042128A1/de active Application Filing
- 2015-09-18 PL PL15771063T patent/PL3194551T3/pl unknown
Also Published As
Publication number | Publication date |
---|---|
US10479962B2 (en) | 2019-11-19 |
WO2016042128A1 (de) | 2016-03-24 |
PL3194551T3 (pl) | 2021-03-08 |
US20170275574A1 (en) | 2017-09-28 |
DE102014218950A1 (de) | 2016-03-24 |
KR20170058399A (ko) | 2017-05-26 |
ES2821819T3 (es) | 2021-04-27 |
EP3194551B1 (de) | 2020-08-12 |
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