EP3167034B1 - Polyalkoxylated polyamines in laundry methods - Google Patents
Polyalkoxylated polyamines in laundry methods Download PDFInfo
- Publication number
- EP3167034B1 EP3167034B1 EP15735697.3A EP15735697A EP3167034B1 EP 3167034 B1 EP3167034 B1 EP 3167034B1 EP 15735697 A EP15735697 A EP 15735697A EP 3167034 B1 EP3167034 B1 EP 3167034B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- washing liquor
- polyalkoxylated
- water
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 10
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- 150000002338 glycosides Chemical class 0.000 description 4
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
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- 239000001530 fumaric acid Substances 0.000 description 1
- LQJBNNIYVWPHFW-QXMHVHEDSA-N gadoleic acid Chemical compound CCCCCCCCCC\C=C/CCCCCCCC(O)=O LQJBNNIYVWPHFW-QXMHVHEDSA-N 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229940059442 hemicellulase Drugs 0.000 description 1
- 108010002430 hemicellulase Proteins 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002951 idosyl group Chemical class C1([C@@H](O)[C@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 150000002584 ketoses Chemical class 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical class COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000021290 n-3 DPA Nutrition 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- CNVZJPUDSLNTQU-OUKQBFOZSA-N petroselaidic acid Chemical compound CCCCCCCCCCC\C=C\CCCCC(O)=O CNVZJPUDSLNTQU-OUKQBFOZSA-N 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229940044652 phenolsulfonate Drugs 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 235000019419 proteases Nutrition 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- DPUOLQHDNGRHBS-MDZDMXLPSA-N trans-Brassidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-MDZDMXLPSA-N 0.000 description 1
- AQWHMKSIVLSRNY-UHFFFAOYSA-N trans-Octadec-5-ensaeure Natural products CCCCCCCCCCCCC=CCCCC(O)=O AQWHMKSIVLSRNY-UHFFFAOYSA-N 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000037303 wrinkles Effects 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
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- 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
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/12—Water-insoluble compounds
- C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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 use of alkoxylated polyamines (also referred to below as PEI) in novel washing processes for enhancing the primary washing power of detergents when washing textile substrates in wash liquors containing such alkoxylated polyamines.
- PEI alkoxylated polyamines
- detergents In addition to the ingredients indispensable for the washing process, such as surfactants and builders, detergents generally contain further constituents, which can be summarized under the term washing aids and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaching agents, bleach activators and color transfer inhibitors.
- Such excipients also include substances whose presence enhances the detergency of surfactants, without them usually having to have a surfactant behavior itself. The same applies mutatis mutandis to cleaners for hard surfaces.
- Such substances are often referred to as a detergency booster or in the case of a particularly pronounced effect against oil or fat-based stains as a "fat booster".
- Alkoxylated polyamines and their use in detergents and cleaners are known, for example, from international patent applications WO 95/32272 A1 and WO 2006/108857 A1 known. From the international patent application WO 2006/108856 For example, amphiphilic water-soluble alkoxylated polyamines having an inner polyethylene block and an outer polypropylene block are known. It is in the DE 10 2011 089 948 A1 already described that certain alkoxylated polyamines with inner polypropylene block and outer polyethylene block have particularly good primary washing power enhancing properties.
- US-A-2005/183206 relates to compositions and methods for cleaning textile substrates, especially carpet and upholstery fabrics.
- the document relates to liquid compositions containing absorbent particles in a flowable liquid dispersion resulting in a soil-loaded powder which can be removed by suction or brushing, drying and / or washing processes.
- EP-A-1371718 discloses polymeric nanoparticles having an average particle diameter of 1 to 10 nm which are included as fabric care additives in detergent formulations to improve properties such as softening, wrinkle resistance, soil and stain removal, soil release, dye transfer, dye fixation, static control and anti-foaming , are suitable.
- the nanoparticles can be used with silicone compounds in the detergent formulation, or can be functionalized with silicone groups to extend significantly different fabric care properties of the formulations.
- US-A-4655952 teaches a detergent and a process for its preparation, the detergent for textile surfaces, in particular of textile floor coverings.
- the product contains a powdered, porous carrier of a foamed, plasticized urea-formaldehyde resin foam enriched with detergent and contains a hydrous surfactant which adheres to the carrier material, the water in the carrier material adhering completely homogeneously.
- JP-A-04241165 relates to the treatment of a dyed natural fiber material having an appearance similar to that of a stone-washed fabric while avoiding the deficiencies of the stone-wash treatment and discloses the treatment of indigo-dyed denim clothing by stirring and washing in water or in an aqueous solution of a detergent Frictional contact with solid rubber balls and 10-50 wt .-% of an abrasive such as MgO with a particle size of 60-200 mesh.
- DE-A-1 900 002 discloses solid detergents, surfactants, detergents, non-surface active cleaning salts and laundry additives containing polymers of vinyl compounds having an average particle size of less than 1 mm.
- WO-A-01/71083 discloses a washing machine having a drum for receiving articles to be washed, the drum having at least two rotatable drum sections and a drive, the drum comprising a plurality of different drum modes, including a mode in which the rotatable drum parts are driven to effect a relative rotation between them.
- a controller controls the apparatus to execute a plurality of different wash programs, each wash program having an associated drum mode.
- WO 2010/094959 A1 relates to the cleaning of substrates using a solvent-free cleaning system which requires the use of only small amounts of water.
- the book deals with the cleaning of textile fibers with the help of such a system, and provides an apparatus for use in this context.
- WO 2007/128962 enables the efficient separation of the substrate from the polymer particles upon completion of the cleaning process and describes a design for using two internal drums.
- the object of the present invention is to improve the washing performance in the presence of a large number of water-insoluble solid particles, preferably polymer particles, in particular in the removal of stains from textile substrates with oily and / or fatty, proteinaceous and / or fruitaceous soils.
- an aqueous wash liquor is suitable for use in a device for cleaning soiled textile substrates containing a plurality of water-insoluble solid polymer particles and a liquid detergent containing polyalkoxylated polyamines and a non-aqueous solvent.
- PEI in combination with the water-insoluble solid particles in the wash liquor according to the invention enhances the primary washing power when washing textiles against, in particular, oil and / or greasy stains or fruit-containing soils.
- PEI shows interactions with anionic surfactants such as in particular alkyl ether sulfate, which may be due to the formation of a surfactant-drug aggregate.
- anionic surfactants such as in particular alkyl ether sulfate
- the effect can be detected by measuring the surface or interfacial tension, the surface or interfacial tension being increased by the presence of the active ingredient. This increase may be due to the formation of a detergent-active aggregate in the solution and therefore less surfactant at the interface.
- the polyalkoxylated polyamine is a polymer having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms.
- the polyamine has primary amino functions at the ends and preferably both secondary and tertiary amino functions inside; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine.
- the ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1.
- the ratio of primary to tertiary amino groups in the polyamine is preferably in the range 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 mean molar masses indicated here and later, if appropriate, for other polymeric ingredients are weight-average molar masses M w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard.
- the N atoms in the polyamine are preferably separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof.
- the primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, with not every amino function having to be substituted by alkoxy groups.
- 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 which are bonded directly to N atoms, and polyethoxy groups, which are bonded to the propoxy radicals and optionally to N atoms which carry no propoxy groups.
- the polyalkoxylated polyamines are accessible by reaction of polyamines with propylene oxide and subsequent reaction with ethylene oxide.
- the average number of propoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 40, especially 5 to 20, and 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, if desired , the terminal OH function Polyalkoxysubstituenten in polyalkoxylated polyamine partially or completely with a C 1 - C 10, in particular C 1 -C 3 - alkyl group etherified be.
- PEI's particularly preferred according to the invention can be selected from PEI's reacted with 43EO, PEI's reacted with 43EO, PEI's reacted with 15EO + 5PO, PEI's reacted with 15PO + 30EO, PEI's reacted with 5PO + 39.5EO, PEI's reacted with 5PO + 15EO, PEI's with 10PO + 35EO, PEI's implemented with 15PO + 30EO and PEI's implemented with 15PO + 5EO.
- ethoxylated and / or propoxylated polyamines have particularly good primary laundry-enhancing properties in combination with the water-insoluble solid particles if the proportion of propoxylene groups in the entirety of the alkoxy groups does not leave a certain range. The effect is particularly pronounced if one seeks the removal of fruitous soils.
- polyalkoxylated polyamines which are obtainable by reacting polyamines with ethylene oxide and propylene oxide, wherein the proportion of propylene oxide in the total amount of the alkylene oxide 2 mol% to 18 mol%, especially 8 mol% to 15 mol% is in the detergents to enhance the primary washing or cleaning power when washing textiles against soiling, especially those with fruit-containing preparations.
- the invention therefore also provides a combination of PEI obtainable by reacting polyamines with alkylene oxide, in particular ethylene oxide and / or propylene oxide, with water-insoluble solid particles and alkoxylated C 8 -C 18 -alcohols having an average degree of alkoxylation in the range from 1 to 5 , especially from 2 to 4, in detergents to enhance the primary washing or cleaning power when washing textile substrates against stains.
- alkylene oxide in particular ethylene oxide and / or propylene oxide
- water-insoluble solid particles and alkoxylated C 8 -C 18 -alcohols having an average degree of alkoxylation in the range from 1 to 5 , especially from 2 to 4, in detergents to enhance the primary washing or cleaning power when washing textile substrates against stains.
- alkoxylated polyamines have particularly good primary wash strength enhancing properties when combined with the water-insoluble solid particles and certain nonionic surfactants.
- the weight ratio of polyalkoxylated polyamine to alkoxylated C 8 -C 18 -alcohol having an average degree of alkoxylation of 1 to 5 is in the range of 1: 3 to 3: 1, in particular 1: 2 to 2: 1.
- Alkoxylated C 8 -C 18 -alcohols in the context of the present invention and their individual aspects are obtainable by reacting corresponding alcohols with alkylene oxide, preference being given to primary linear or branched-chain alcohols.
- the alkoxylates of primary alcohols having linear, in particular decyl, dodecyl, tridecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are useful.
- the alcohol has a maximum of 16 C atoms, in particular 12 to 14 C atoms.
- the degree of alkoxylation, that is the average number of alkoxy groups per alcohol function, of the lower alkoxylated alcohol can be integer or fractional and preferably in the range from 2 to 4, in particular from 2 to 3.5.
- Preferred alkoxy groups are ethoxy, propoxy and butoxy groups, especially ethoxy groups and mixtures of ethoxy and propoxy groups.
- An embodiment of the invention is therefore the use of the wash liquor according to the invention for the removal of proteinaceous soils, such as blood, egg, milk, or stains proteinaceous preparations, such as chocolate, latte, pudding.
- proteinaceous soils such as blood, egg, milk, or stains proteinaceous preparations, such as chocolate, latte, pudding.
- the invention encompasses the removal of stains, in particular protein-containing stains or soiling of proteinaceous preparations, of textile substrates in which a wash liquor containing a combination of polyalkoxylated polyamine, water-insoluble solid particles and, optionally, low alkoxylated alcohol is used.
- Fruit-containing preparations are nutritionally suitable fruit preparations, such as jams, jams and jellies. These lead due to their thickener content and their fruit content to difficult to remove stains.
- This wash liquor can be obtained manually or preferably by machine, for example by means of a washing machine. It is possible to apply a solid or liquid detergent beforehand, simultaneously or after use with the water-insoluble solid particles.
- the concentration of said polyalkoxylated polyamine in the liquid fraction of the wash liquor according to the invention including the water-insoluble solid particles is preferably 1 mg / l to 500 mg / l, in particular 5 mg / l to 100 mg / l.
- the liquid portion of the wash liquor is understood as the proportion of the total wash liquor including the water-insoluble solid particles obtained by centrifuging 8 kg of the wash liquor containing the solid water-insoluble particles for 5 minutes in a centrifuge with the water-insoluble solid particles separated cylindrical rotating body of 515 mm inner diameter and 370 mm internal depth at 1400 revolutions per minute from the liquid portion.
- the detergent contains at least one surfactant in addition to the PEI.
- the PEI-containing detergent preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20 wt .-%, in particular from 0.1 wt .-% to 18 wt .-%, each based on the total agent.
- Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation.
- the alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
- a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
- the sulfate-type surfactants which can be used with particular preference include the abovementioned sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
- Such ether sulfates preferably contain 2 to 30, in particular 4 to 10 ethylene glycol groups per molecule.
- Suitable anionic surfactants of the sulfonate type include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.
- the anionic surfactants which can be used also include the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant.
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- Another synthetic anionic surfactant is alkylbenzenesulfonate in question.
- a further preferred embodiment of the detergents comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides their mixtures, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
- nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and /
- Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms.
- the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
- Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
- alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
- suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
- the ethylene oxide and / or propylene oxide insertion products come of fatty acid alkyl esters and Fettklarepolyhydroxyamiden into consideration.
- alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) n -OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
- the glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose.
- the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomermaschinesgrad.
- the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
- Preferred monomer building block is glucose because of its good availability.
- the alkyl or alkenyl moiety R 12 of the glycosides preferably also originates from readily available derivatives of the raw materials, in particular fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used to prepare useful glycosides.
- the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable.
- soaps suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
- those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
- soap is included in amounts of from 0.1% to 5% by weight.
- higher amounts of soap can be contained, usually up to 20 wt .-%.
- the detergents may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% to 7% by weight. Among these, esterquats are particularly preferred.
- the detergents may contain peroxygen bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, especially in amounts ranging from 2% to 10% by weight.
- the bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts.
- Such bleaching agents are in detergents containing an active ingredient according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on total agent, present, in particular percarbonate is used.
- the optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammoniumacetonitrile salts.
- N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetyl
- the bleach activators may have been coated and / or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or in particulate form, trialkylammonium acetonitrile is particularly preferred.
- Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
- the detergent contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
- the detergent preferably contains from 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
- the water-soluble organic builder substances include, in particular, those from the class of polycarboxylic acids, in particular citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also small proportions of polymerizable substances without carboxylic acid functionality may contain polymerized.
- the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid ,
- a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to 100,000 g / mol.
- Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. It is also possible to use as water-soluble organic builder substances terpolymers which contain two carboxylic acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer.
- the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
- the second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred.
- the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
- Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
- the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted.
- Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt. % of a carbohydrate.
- This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
- the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
- These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol.
- polycarboxylic acids can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions.
- All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
- Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
- Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
- the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
- suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
- Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates which may be present alone or in a mixture with amorphous silicates.
- the alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
- Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
- Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar ratio of Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 are preferably added in the course of the production as a solid and not in the form of a solution.
- the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + 1 ⁇ are used yH 2 O, in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
- Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 A described.
- Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates are (Na 2 Si 2 O 5 .yH 2 O) is preferred.
- amorphous alkali metal silicates practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1.9 to 2.1, can be used in agents which contain an active ingredient to be used according to the invention.
- a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention.
- alkali metal silicates are preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
- the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
- water-soluble or water-insoluble inorganic substances may be contained in the detergents which contain an active substance to be used according to the invention, used together with the latter or used in processes according to the invention.
- Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof.
- Such additional inorganic material may be present in amounts up to 70% by weight.
- the detergents may contain other usual in detergents or cleaning ingredients.
- These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
- agents which contain an active substance used according to the invention up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular aminoalkylenephosphonic acids and their salts and up to 2% by weight, in particular 0.1% by weight contain up to 1 wt .-% foam inhibitors, wherein said weight fractions each refer to the total agent.
- optical brighteners in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular
- the nonaqueous solvents are preferably those nonaqueous solvents that are water miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether.
- the active compounds used in the invention are usually dissolved or in suspended form.
- Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof.
- proteases derived from microorganisms such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms.
- Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
- the lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species.
- Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase.
- Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm.
- the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
- Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
- Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
- enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.
- Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica.
- foam inhibitors are preferably bound to granular, water-soluble carrier substances.
- polyester-active soil release polymers which can be used in addition to the active compounds of the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
- dicarboxylic acids for example adipic acid, phthalic acid or terephthalic acid
- diols for example ethylene glycol or propylene glycol
- polydiols for example polyethylene glycol or polypropylene glycol.
- Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
- Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
- R 11 denotes hydrogen
- a is a number from 2 to 6
- b is a number from 1 to 300.
- the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
- the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140.
- the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyesters is in the range of 250 g / mol to 100,000 g / mol , in particular from 500 g / mol to 50,000 g / mol.
- the acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
- acids having at least two carboxyl groups may be included in the soil release-capable polyester.
- these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
- the preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
- R 11 is hydrogen and a is a number from 2 to 6
- R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
- those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
- diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
- Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol.
- these polyesters composed as described above may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
- the ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonklaren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based.
- valeric acid caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butyl
- the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
- the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
- the soil release polymers are preferably water-soluble, wherein the term "water-soluble" has a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water Room temperature and pH 8 should be understood.
- preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.
- the preparation of solid detergents presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, with enzymes and any other thermally-sensitive ingredients such as, for example, bleaching agents optionally being added separately later.
- a process comprising an extrusion step is preferred.
- a PEI-containing liquid detergent contains 1 wt .-% to 15 wt .-%, in particular 2 wt .-% to 10 wt .-% of nonionic surfactant, 2 wt .-% to 30 wt .-%, in particular from 5% by weight to 20% by weight of synthetic anionic surfactant, up to 15% by weight, in particular from 2% by weight to 12.5% by weight, of soap, from 0.5% by weight to 5% by weight.
- organic builder in particular polycarboxylate such as citrate, up to 1.5 wt .-%, in particular 0.1 wt .-% to 1 wt .-% complexing agent for heavy metals such as phosphonate, and optionally enzyme, enzyme stabilizer, color and / or perfume, water and / or water-miscible solvent.
- the detergent is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, of up to 15% by weight, in particular 1% by weight. to 10% by weight of bleach activator, 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular 2% by weight to 8% by weight, of water-soluble organic builder, 10% by weight % to 25 wt .-% of synthetic anionic surfactant, 1 wt .-% to 5 wt .-% of nonionic surfactant and up to 25 wt .-%, in particular 0.1 wt .-% to 25 wt .-% of inorganic salts, in particular Alkali carbonate and / or bicarbonate.
- bleaching agent in particular alkali percarbonate
- the detergent is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleaching agent, in particular alkali per
- Another aspect of the present invention includes a method of cleaning a soiled textile substrate, the method including treating the wet substrate with the above formulation comprising a plurality of water-insoluble solid polymer particles, wherein the polymer particles are optionally regenerated with or be reused without the use of the detergent in further purification processes according to the method.
- the PEI-containing detergent can be introduced into the device before the polymer particles are brought into contact with the soiled textile substrate (wetting with water) during, before or after contacting the polymer particles with the substrate.
- the detergent or the water-insoluble solid particles in incremental steps.
- the substrate to be cleaned according to the invention comprises textile substrates, each optionally of a variety of materials, which may be either a natural fiber such as cotton or synthetic textile fibers such as nylon 6,6 or a polyester.
- polymer particles are polyalkenes such as polyethylene and polypropylene, polyesters and polyurethanes.
- polymer particles of polyamide more particularly particles of nylon, most preferably in the form of nylon chips.
- the polyamides are particularly effective for aqueous stain / soil removal, while polyalkenes are particularly useful for removing oily stains.
- copolymers of the above polymeric materials may be used for the purposes of the invention.
- nylon 6 Various nylon homo- or co-polymers can be used, including nylon 6 and nylon 6,6.
- the polyamide comprises nylon 6,6 homopolymer having an average molecular weight in the range of 5,000 to 30,000 daltons, preferably 10,000 to 20,000 daltons, most preferably 15,000 to 16,000 daltons.
- the water-insoluble solid particles or granules, particles or moldings are of such a shape and size that enables good flowability and close contact with the textile substrate.
- Preferred forms of the particles include spheres and cubes, but the preferred particle shape is cylindrical.
- the particles are preferably sized to each have an average weight in the range of 20-50 mg, preferably 30-40 mg.
- the preferred average particle diameter is 1.5 to 6.0 mm, more preferably 2.0 to 5.0 mm, most preferably 2.5 to 4.5 mm, while the length of the cylindrical particles is preferably in the range of 2.0 to 6.0 mm, more preferably 3.0 to 5.0 mm, and most preferably in the range of 4.0 mm.
- the textile substrate Prior to cleaning, the textile substrate is preferably moistened by wetting with water to provide additional enhancement to the wash liquor thereby allowing for an improvement in transport properties within the system (Pretreatment).
- Pretreatment more efficient transfer from the detergent to the substrate and the removal of soils and stains from the substrate is facilitated.
- the substrate can be wetted by contact with tap water.
- the wetting treatment is carried out to achieve a substrate to water weight ratio of 1: 0.1 to 1: 5; more preferably the ratio is between 1: 0.2 and 1: 2, with particularly favorable results being achieved in ratios such as 1: 0.2, 1: 1 and 1: 2.
- successful results with the substrate can be achieved to water ratios of up to 1:50, although such ratios are not preferred in view of the significant amounts of wastewater that are generated.
- a weight ratio of textile substrate to water-insoluble solid particles in the range of 1: 1 to 1:30, in particular from 1: 1.5 to 1: 2.5, especially set by 1: 2.
- the water-insoluble solid particles can be coated prior to use with the detergent according to known methods.
- the regeneration of the water-insoluble solid particles can be carried out in a conventional manner, as described for example in the WO 2012/035342 A1 is described.
- the regeneration is carried out by contacting the particles with the detergent, for example by coating the particles with the agent, for example in a separate rinse, optionally by adding further cleaning agents, which may also be aggressive in nature.
- the temperature of the regeneration step is independent of the washing temperature when the textile substrate has been removed from the washing machine before regeneration.
- the usual detergent raw materials can be used.
- Another embodiment of the invention involves the regeneration of the water-insoluble, solid polymer particles as described in claim 14.
- a further embodiment of the invention comprises the use of a plurality of water-insoluble solid particles as defined above, and a PEI-containing detergent for cleaning textile substrates by contacting the detergent and the particles with the textile substrate as described in claim 12.
- a device for cleaning soiled textile substrates comprising a plurality of water-insoluble solid particles, a reservoir for receiving the particles inside or outside the device, and a detergent containing polyalkoxylated polyamines is also disclosed.
- An essential feature of the device is the presence of the above water-insoluble solid particles, a reservoir for the particles and the polyalkoxylated polyamine-containing detergent as described above.
- the apparatus typically includes a trap door in a housing to allow access to the interior of the washing tub to provide a substantially closed system.
- the door includes a window of the stationary cylindrical drum rotatably supported in another drum while the rotatably supported cylinder drum is mounted vertically inside the housing. Consequently, a front loading device is preferred.
- the stationary cylindrical drum may be mounted vertically within the housing and the access device located in the top of the device.
- the device is suitable for providing contact of the particles with the soiled substrate. Ideally, these particles should be efficiently circulated to promote effective purification.
- the apparatus comprises at least one reservoir, in particular with a corresponding control, for the water-insoluble solid particles, for example located inside the washing machine, which contains particles for regeneration and is suitable for controlling the flow of particles within the washing machine.
- Table 1 Detergent compositions (in% by weight) A B C D e F G H C9-13-Alkylbenzenesulfonate, Na salt 9 10 6 7 5 15 15 9 C12-18 fatty alcohol with 7 EO 8th 9 6 7 5 6 11 10 C12-14 fatty alcohol sulfate with 2EO - - 8th 7 10 2 2 5 C12-18 fatty acid, Na salt 4 3 3 3 4 2 4 7 citric acid 2 3 3 2 2 2 2 3 Sodium hydroxide, 50% 3 3 2 3 3 3 3 4 boric acid 1 1 1 1 1 1 1 1 1 1 1 enzymes + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +
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Description
Die vorliegende Erfindung betrifft den Einsatz alkoxylierter Polyamine (im Folgenden auch PEI genannt) in neuartigen Waschverfahren zur Verstärkung der Primärwaschkraft von Waschmitteln beim Waschen von textilen Substraten in Waschflotten, welche derartige alkoxylierte Polyamine enthalten.The present invention relates to the use of alkoxylated polyamines (also referred to below as PEI) in novel washing processes for enhancing the primary washing power of detergents when washing textile substrates in wash liquors containing such alkoxylated polyamines.
Waschmittel enthalten neben den für den Waschprozess unverzichtbaren Inhaltsstoffen wie Tensiden und Buildermaterialien in der Regel weitere Bestandteile, die man unter dem Begriff Waschhilfsstoffe zusammenfassen kann und die so unterschiedlichen Wirkstoffgruppen wie Schaumregulatoren, Vergrauungsinhibitoren, Bleichmittel, Bleichaktivatoren und Farbübertragungsinhibitoren umfassen. Zu derartigen Hilfsstoffen gehören auch Substanzen, deren Anwesenheit die Waschkraft von Tensiden verstärkt, ohne dass sie in der Regel selbst ein tensidisches Verhalten aufweisen müssen. Gleiches gilt sinngemäß auch für Reinigungsmittel für harte Oberflächen. Derartige Substanzen werden oft als Waschkraftverstärker oder im Fall einer besonders ausgeprägten Wirkung gegenüber öl- oder fettbasierten Anschmutzungen als "Fatbooster" bezeichnet.In addition to the ingredients indispensable for the washing process, such as surfactants and builders, detergents generally contain further constituents, which can be summarized under the term washing aids and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such excipients also include substances whose presence enhances the detergency of surfactants, without them usually having to have a surfactant behavior itself. The same applies mutatis mutandis to cleaners for hard surfaces. Such substances are often referred to as a detergency booster or in the case of a particularly pronounced effect against oil or fat-based stains as a "fat booster".
Alkoxylierte Polyamine und ihr Einsatz in Wasch- und Reinigungsmitteln sind beispielsweise aus den internationalen Patentanmeldungen
Aufgabe der vorliegenden Erfindung ist die Verbesserung der Waschleistung bei Anwesenheit einer Vielzahl von wasserunlöslichen festen Teilchen, vorzugsweise Polymerteilchen, insbesondere bei der Entfernung von Flecken von textilen Substraten mit öl- und/oder fetthaltigen, proteinhaltigen und/oder fruchthaltigen Anschmutzungen.The object of the present invention is to improve the washing performance in the presence of a large number of water-insoluble solid particles, preferably polymer particles, in particular in the removal of stains from textile substrates with oily and / or fatty, proteinaceous and / or fruitaceous soils.
Gegenstand der Erfindung in einer ersten Ausführungsform ist eine wässrige Waschflotte geeignet zur Verwendung in einer Vorrichtung zur Reinigung von verschmutzten textilen Substraten enthaltend eine Vielzahl von wasserunlöslichen festen Polymerteilchen und ein flüssiges Waschmittel, das polyalkoxylierte Polyamine und ein nicht-wässriges Lösemittel enthält.The invention in a first embodiment, an aqueous wash liquor is suitable for use in a device for cleaning soiled textile substrates containing a plurality of water-insoluble solid polymer particles and a liquid detergent containing polyalkoxylated polyamines and a non-aqueous solvent.
Die Verwendung der PEI bewirkt in Kombination mit den wasserunlöslichen festen Teilchen in der erfindungsgemäßen Waschflotte eine Verstärkung der Primärwaschkraft beim Waschen von Textilien gegenüber insbesondere öl- und/oder fetthaltigen Anschmutzungen oder fruchthaltigen Anschmutzungen.The use of PEI in combination with the water-insoluble solid particles in the wash liquor according to the invention enhances the primary washing power when washing textiles against, in particular, oil and / or greasy stains or fruit-containing soils.
PEI zeigt Wechselwirkungen mit anionischen Tensiden wie insbesondere Alkylethersulfat, die auf die Ausbildung eines Tensid- Wirkstoff-Aggregats zurückzuführen sein können. Der Effekt kann über eine Messung der Oberflächen- oder Grenzflächenspannung nachgewiesen werden, wobei die Oberflächen- oder Grenzflächenspannung durch die Anwesenheit des Wirkstoffs erhöht wird. Diese Erhöhung kann darauf beruhen, dass sich ein reinigungsaktives Aggregat in der Lösung bildet und daher weniger Tensid an der Grenzfläche vorhanden ist.PEI shows interactions with anionic surfactants such as in particular alkyl ether sulfate, which may be due to the formation of a surfactant-drug aggregate. The effect can be detected by measuring the surface or interfacial tension, the surface or interfacial tension being increased by the presence of the active ingredient. This increase may be due to the formation of a detergent-active aggregate in the solution and therefore less surfactant at the interface.
Bei dem polyalkoxylierten Polyamin im Rahmen der vorliegenden Erfindung und deren einzelner Aspekte handelt es sich um ein Polymer mit einem N-Atom-haltigen Rückgrat, das an den N-Atomen Polyalkoxygruppen trägt. Das Polyamin weist an den Enden primäre Aminofunktionen und im Inneren vorzugsweise sowohl sekundäre als auch tertiäre Aminofunktionen auf; gegebenenfalls kann es im Inneren auch lediglich sekundäre Aminofunktionen aufweisen, so dass sich nicht ein verzweigtkettiges, sondern ein lineares Polyamin ergibt. Das Verhältnis von primären zu sekundären Aminogruppen im Polyamin liegt vorzugsweise im Bereich von 1:0,5 bis 1:1,5, insbesondere im Bereich von 1:0,7 bis 1:1. Das Verhältnis von primären zu tertiären Aminogruppen im Polyamin liegt vorzugsweise im Bereich von 1:0,2 bis 1:1, insbesondere im Bereich von 1:0,5 bis 1:0,8. Vorzugsweise weist das Polyamin eine mittlere Molmasse im Bereich von 500 g/mol bis 50000 g/mol, insbesondere von 550 g/mol bis 5000 g/mol auf. Bei den hier und später gegebenenfalls für andere polymere Inhaltsstoffe angegebenen mittleren Molmassen handelt es sich um gewichtsmittlere Molmassen Mw, die grundsätzlich mittels Gelpermeationschromatographie mit Hilfe eines RI-Detektors bestimmbar sind, wobei die Messung zweckmäßig gegen einen externen Standard erfolgt. Die N-Atome im Polyamin sind vorzugsweise durch Alkylengruppen mit 2 bis 12 C-Atomen, insbesondere 2 bis 6 C-Atomen, voneinander getrennt, wobei nicht sämtliche Alkylengruppen die gleiche C-Atomzahl aufweisen müssen. Besonders bevorzugt sind Ethylengruppen, 1,2-Propylengruppen, 1,3-Propylengruppen, und deren Mischungen. Die primären Aminofunktionen im Polyamin können 1 oder 2 Polyalkoxygruppen und die sekundären Aminofunktionen 1 Polyalkoxygruppe tragen, wobei nicht jede Aminofunktion Alkoxygruppensubstituiert sein muss. Die durchschnittliche Anzahl von Alkoxygruppen pro primärer und sekundärer Aminofunktion im polyalkoxylierten Polyamin beträgt vorzugsweise 1 bis 100, insbesondere 5 bis 50. Bei den Alkoxygruppen im polyalkoxylierten Polyamin handelt es sich vorzugsweise um Polypropoxygruppen, die direkt an N-Atome gebunden sind, und um Polyethoxygruppen, die an die Propoxyreste und gegebenenfalls an N-Atome gebunden sind, welche keine Propoxygruppen tragen. Die polyalkoxylierten Polyamine sind durch Umsetzung von Polyaminen mit Propylenoxid und nachfolgende Umsetzung mit Ethylenoxid zugänglich. Die durchschnittliche Anzahl von Propoxygruppen pro primärer und sekundärer Aminofunktion im polyalkoxylierten Polyamin beträgt vorzugsweise 1 bis 40, insbesondere 5 bis 20, und die durchschnittliche Anzahl von Ethoxygruppen pro primärer und sekundärer Aminofunktion im polyalkoxylierten Polyamin beträgt vorzugsweise 10 bis 60, insbesondere 15 bis 30. Gewünschtenfalls kann die endständige OH-Funktion Polyalkoxysubstituenten im polyalkoxylierten Polyamin teilweise oder vollständig mit einer C1 - C10, insbesondere C1-C3- Alkylgruppe verethert sein. Erfindungsgemäß besonders bevorzugte PEI's können ausgewählt sein aus PEI's umgesetzt mit 45EO, PEI's umgesetzt mit 43EO, PEI's umgesetzt mit 15EO + 5PO, PEI's umgesetzt mit 15PO + 30EO, PEI's umgesetzt mit 5PO + 39,5EO, PEI's umgesetzt mit 5PO + 15EO, PEI's umgesetzt mit 10PO + 35EO, PEI's umgesetzt mit 15PO + 30EO und PEI's umgesetzt mit 15PO + 5EO.In the context of the present invention and its individual aspects, the polyalkoxylated polyamine is a polymer having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms. The polyamine has primary amino functions at the ends and preferably both secondary and tertiary amino functions inside; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine. The ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1. The ratio of primary to tertiary amino groups in the polyamine is preferably in the range of 1: 0.2 to 1: 1, in particular in the range of 1: 0.5 to 1: 0.8. Preferably, the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol. The mean molar masses indicated here and later, if appropriate, for other polymeric ingredients are weight-average molar masses M w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard. The N atoms in the polyamine are preferably separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof. The primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, with not every amino function having to be substituted by alkoxy groups. 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 which are bonded directly to N atoms, and polyethoxy groups, which are bonded to the propoxy radicals and optionally to N atoms which carry no propoxy groups. The polyalkoxylated polyamines are accessible by reaction of polyamines with propylene oxide and subsequent reaction with ethylene oxide. The average number of propoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 40, especially 5 to 20, and 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, if desired , the terminal OH function Polyalkoxysubstituenten in polyalkoxylated polyamine partially or completely with a C 1 - C 10, in particular C 1 -C 3 - alkyl group etherified be. PEI's particularly preferred according to the invention can be selected from PEI's reacted with 43EO, PEI's reacted with 43EO, PEI's reacted with 15EO + 5PO, PEI's reacted with 15PO + 30EO, PEI's reacted with 5PO + 39.5EO, PEI's reacted with 5PO + 15EO, PEI's with 10PO + 35EO, PEI's implemented with 15PO + 30EO and PEI's implemented with 15PO + 5EO.
Weiterhin wurde hier gefunden, dass ethoxylierte und/oder propoxylierte Polyamine dann besonders gute die Primärwaschkraft verstärkende Eigenschaften in Kombination mit den waserunlöslichen festen Teilchen aufweisen, wenn der Anteil an Propoxylengruppen an der Gesamtheit der Alkoxylengruppen einen bestimmten Bereich nicht verlässt. Der Effekt ist besonders ausgeprägt, wenn man die Entfernung fruchthaltiger Anschmutzungen anstrebt. Weiterhin bevorzugter Gegenstand der Erfindung ist der Einsatz von polyalkoxylierten Polyaminen, die erhältlich sind durch Umsetzung von Polyaminen mit Ethylenoxid und Propylenoxid, wobei der Anteil an Propylenoxid an der Gesamtmenge des Alkylenoxids 2 Mol-% bis 18 Mol-%, insbesondere 8 Mol-% bis 15 Mol-% beträgt, in den Waschmitteln zur Verstärkung der Primärwasch- oder Reinigungskraft beim Waschen von Textilien gegenüber Anschmutzungen, insbesondere solcher mit fruchthaltigen Zubereitungen.Furthermore, it has been found here that ethoxylated and / or propoxylated polyamines have particularly good primary laundry-enhancing properties in combination with the water-insoluble solid particles if the proportion of propoxylene groups in the entirety of the alkoxy groups does not leave a certain range. The effect is particularly pronounced if one seeks the removal of fruitous soils. Further preferred subject of the invention is the use of polyalkoxylated polyamines, which are obtainable by reacting polyamines with ethylene oxide and propylene oxide, wherein the proportion of propylene oxide in the total amount of the alkylene oxide 2 mol% to 18 mol%, especially 8 mol% to 15 mol% is in the detergents to enhance the primary washing or cleaning power when washing textiles against soiling, especially those with fruit-containing preparations.
Gegenstand der Erfindung ist daher auch eine Kombination aus PEI, die erhältlich sind durch Umsetzung von Polyaminen mit Alkylenoxid, insbesondere Ethylenoxid und/oder Propylenoxid, mit wasserunlöslichen festen Teilchen und alkoxylierten C8-C18-Alkoholen mit durchschnittlichem Alkoxylierungsgrad im Bereich von 1 bis 5, insbesondere von 2 bis 4, in Waschmitteln zur Verstärkung der Primärwasch- oder Reinigungskraft beim Waschen von textilen Substraten gegenüber Anschmutzungen.The invention therefore also provides a combination of PEI obtainable by reacting polyamines with alkylene oxide, in particular ethylene oxide and / or propylene oxide, with water-insoluble solid particles and alkoxylated C 8 -C 18 -alcohols having an average degree of alkoxylation in the range from 1 to 5 , especially from 2 to 4, in detergents to enhance the primary washing or cleaning power when washing textile substrates against stains.
Weiterhin wurde gefunden, dass alkoxylierte Polyamine dann besonders gute die Primärwaschkraft verstärkende Eigenschaften aufweisen, wenn man sie mit den wasserunlöslichen festen Teilchen und bestimmten nichtionischen Tensiden kombiniert.Furthermore, it has been found that alkoxylated polyamines have particularly good primary wash strength enhancing properties when combined with the water-insoluble solid particles and certain nonionic surfactants.
Vorzugsweise liegt das Gewichtsverhältnis von polyalkoxyliertem Polyamin zu alkoxyliertem C8-C18-Alkohol mit durchschnittlichem Alkoxylierungsgrad von 1 bis 5 im Bereich von 1:3 bis 3:1, insbesondere 1:2 bis 2:1. Alkoxylierte C8-C18-Alkohole im Rahmen der vorliegenden Erfindung und deren einzelner Aspekte sind durch Umsetzung von entsprechenden Alkoholen mit Alkylenoxid zugänglich, wobei primäre lineare oder verzweigtkettige Alkohole bevorzugt sind. Brauchbar sind demgemäß die Alkoxylate primärer Alkohole mit linearen, insbesondere Decyl-, Dodecyl-, Tridecyl-, Tetradecyl-, Hexadecyl- oder Octadecyl-Resten sowie deren Gemische. In bevorzugten Ausführungsformen der Erfindung besitzt der Alkohol maximal 16 C-Atome, insbesondere 12 bis 14 C-Atome. Der Alkoxylierungsgrad, das heißt die durchschnittliche Anzahl von Alkoxygruppen pro Alkoholfunktion, des niedrig alkoxylierten Alkohols kann ganzzahlige oder gebrochene Zahlenwerte annehmen und liegt vorzugsweise im Bereich von 2 bis 4, insbesondere von 2 bis 3,5. Bevorzugte Alkoxygruppen sind Ethoxy-, Propoxy- und Butoxygruppen, insbesondere Ethoxygruppen und Mischungen aus Ethoxy- und Propoxygruppen.Preferably, the weight ratio of polyalkoxylated polyamine to alkoxylated C 8 -C 18 -alcohol having an average degree of alkoxylation of 1 to 5 is in the range of 1: 3 to 3: 1, in particular 1: 2 to 2: 1. Alkoxylated C 8 -C 18 -alcohols in the context of the present invention and their individual aspects are obtainable by reacting corresponding alcohols with alkylene oxide, preference being given to primary linear or branched-chain alcohols. Accordingly, the alkoxylates of primary alcohols having linear, in particular decyl, dodecyl, tridecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are useful. In preferred embodiments of the invention, the alcohol has a maximum of 16 C atoms, in particular 12 to 14 C atoms. The degree of alkoxylation, that is the average number of alkoxy groups per alcohol function, of the lower alkoxylated alcohol can be integer or fractional and preferably in the range from 2 to 4, in particular from 2 to 3.5. Preferred alkoxy groups are ethoxy, propoxy and butoxy groups, especially ethoxy groups and mixtures of ethoxy and propoxy groups.
Eine Ausführungsform der Erfindung ist daher der Einsatz der erfindungsgemäßen Waschflotte zur Entfernung von proteinhaltigen Anschmutzungen, wie beispielsweise Blut, Ei, Milch, oder Anschmutzungen proteinhaltiger Zubereitungen, wie beispielsweise Schokolade, Milchkaffee, Pudding.An embodiment of the invention is therefore the use of the wash liquor according to the invention for the removal of proteinaceous soils, such as blood, egg, milk, or stains proteinaceous preparations, such as chocolate, latte, pudding.
Die Erfindung umfasst das Entfernen von Anschmutzungen, insbesondere proteinhaltigen Anschmutzungen oder Anschmutzungen proteinhaltiger Zubereitungen, von textilen Substraten, bei dem eine Waschflotte, enthaltend eine genannte Kombination aus polyalkoxyliertem Polyamin, wasserunlöslichen festen Teilchen und gegebenenfalls niedrig alkoxyliertem Alkohol zum Einsatz kommen.The invention encompasses the removal of stains, in particular protein-containing stains or soiling of proteinaceous preparations, of textile substrates in which a wash liquor containing a combination of polyalkoxylated polyamine, water-insoluble solid particles and, optionally, low alkoxylated alcohol is used.
Unter fruchthaltigen Zubereitungen werden zur Ernährung geeignete Zubereitungen aus Obst verstanden, wie zum Beispiel Marmeladen, Konfitüren und Gelees. Diese führen aufgrund ihres Verdickergehaltes und ihres Fruchtanteils zu schwierig zu entfernenden Anschmutzungen. Diese Waschflotte kann manuell oder bevorzugt maschinell, zum Beispiel mit Hilfe einer Waschmaschine, erhalten werden. Dabei ist es möglich, ein festes oder flüssiges Waschmittel vorher, gleichzeitig oder nach dem Einsatz mit den wasserunlöslichen festen Teilchen anzuwenden. Die Konzentration des genannten polyalkoxylierten Polyamins in dem flüssigen Anteil der erfindungsgemäßen Waschflotte inklusive der wasserunlöslichen festen Teilchen beträgt vorzugsweise 1 mg/l bis 500 mg/l, insbesondere 5 mg/l bis 100 mg/l. Dabei versteht sich der flüssige Anteil der Waschflotte als der Anteil der gesamten Waschflotte inklusive der wasserunlöslichen festen Teilchen, der erhalten wird, wenn man die wasserunlöslichen festen Teilchen mittels Zentrifugieren von 8 kg der die festen wasserunlöslichen Teilchen enthaltenden Waschflotte für 5 Minuten in einer Zentrifuge mit horizontal montiertem zylindrischen Drehkörper von 515 mm Innendurchmesser und 370 mm innerer Tiefe bei 1400 Umdrehungen pro Minute von dem flüssigen Anteil abtrennt.Fruit-containing preparations are nutritionally suitable fruit preparations, such as jams, jams and jellies. These lead due to their thickener content and their fruit content to difficult to remove stains. This wash liquor can be obtained manually or preferably by machine, for example by means of a washing machine. It is possible to apply a solid or liquid detergent beforehand, simultaneously or after use with the water-insoluble solid particles. The concentration of said polyalkoxylated polyamine in the liquid fraction of the wash liquor according to the invention including the water-insoluble solid particles is preferably 1 mg / l to 500 mg / l, in particular 5 mg / l to 100 mg / l. In this case, the liquid portion of the wash liquor is understood as the proportion of the total wash liquor including the water-insoluble solid particles obtained by centrifuging 8 kg of the wash liquor containing the solid water-insoluble particles for 5 minutes in a centrifuge with the water-insoluble solid particles separated cylindrical rotating body of 515 mm inner diameter and 370 mm internal depth at 1400 revolutions per minute from the liquid portion.
In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung enthält das Waschmittel zusätzlich zu dem PEI mindestens ein Tensid. Das PEI enthaltende Waschmittel enthält vorzugsweise synthetische Aniontenside des Sulfat- oder Sulfonat-Typs, in Mengen von vorzugsweise nicht über 20 Gew.-%, insbesondere von 0,1 Gew.-% bis 18 Gew.-%, jeweils bezogen auf gesamtes Mittel. Als für den Einsatz in derartigen Mitteln besonders geeignete synthetische Aniontenside sind die Alkyl- und/oder Alkenylsulfate mit 8 bis 22 C-Atomen, die ein Alkali-, Ammonium- oder Alkyl- oder Hydroxyalkyl-substituiertes Ammoniumion als Gegenkation tragen, zu nennen. Bevorzugt sind die Derivate der Fettalkohole mit insbesondere 12 bis 18 C-Atomen und deren verzweigtkettiger Analoga, der sogenannten Oxoalkohole. Die Alkyl- und Alkenylsulfate können in bekannter Weise durch Reaktion der entsprechenden Alkoholkomponente mit einem üblichen Sulfatierungsreagenz, insbesondere Schwefeltrioxid oder Chlorsulfonsäure, und anschließende Neutralisation mit Alkali-, Ammonium- oder Alkyl- oder Hydroxyalkylsubstituierten Ammoniumbasen hergestellt werden. Zu den besonders bevorzugt einsetzbaren Tensiden vom Sulfat-Typ gehören die oben erwähnten sulfatierten Alkoxylierungsprodukte der genannten Alkohole, so genannte Ethersulfate. Vorzugsweise enthalten derartige Ethersulfate 2 bis 30, insbesondere 4 bis 10 Ethylenglykol-Gruppen pro Molekül. Zu den geeigneten Aniontensiden vom Sulfonat-Typ gehören die durch Umsetzung von Fettsäureestern mit Schwefeltrioxid und anschließender Neutralisation erhältlichen α-Sulfoester, insbesondere die sich von Fettsäuren mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, und linearen Alkoholen mit 1 bis 6 C-Atomen, vorzugsweise 1 bis 4 C-Atomen, ableitenden Sulfonierungsprodukte, sowie die durch formale Verseifung aus diesen hervorgehenden Sulfofettsäuren. Zu den einsetzbaren Aniontensiden sind auch die Salze von Sulfobernsteinsäurestern zu rechnen, die auch als Alkylsulfosuccinate oder Dialkylsulfosuccinate bezeichnet werden, und die Monoester oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8- bis C18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen ethoxylierten Fettalkoholrest, der für sich betrachtet ein nichtionisches Tenside darstellt. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Als weiteres synthetisches Aniontensid kommt Alkylbenzolsulfonat in Frage.In a further preferred embodiment of the present invention, the detergent contains at least one surfactant in addition to the PEI. The PEI-containing detergent preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20 wt .-%, in particular from 0.1 wt .-% to 18 wt .-%, each based on the total agent. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants which can be used with particular preference include the abovementioned sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10 ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids. The anionic surfactants which can be used also include the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Another synthetic anionic surfactant is alkylbenzenesulfonate in question.
Eine weitere bevorzugte Ausführungsform der Waschmittel umfasst die Anwesenheit von nichtionischem Tensid, ausgewählt aus Fettalkylpolyglykosiden, Fettalkylpolyalkoxylaten, insbesondere -ethoxylaten und/oder-propoxylaten, Fettsäurepolyhydroxyamiden und/oder Ethoxylierungs- und/oder Propoxylierungsprodukten von Fettalkylaminen, vicinalen Diolen, Fettsäurealkylestern und/oder Fettsäureamiden sowie deren Mischungen, insbesondere in einer Menge im Bereich von 2 Gew.-% bis 25 Gew.-%.A further preferred embodiment of the detergents comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides their mixtures, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.
Zu den in Frage kommenden nichtionischen Tensiden gehören die Alkoxylate, insbesondere die Ethoxylate und/oder Propoxylate von gesättigten oder ein- bis mehrfach ungesättigten linearen oder verzweigtkettigen Alkoholen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen. Der Alkoxylierungsgrad der Alkohole liegt dabei in der Regel zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Sie können in bekannter Weise durch Umsetzung der entsprechenden Alkohole mit den entsprechenden Alkylenoxiden hergestellt werden. Geeignet sind insbesondere die Derivate der Fettalkohole, obwohl auch deren verzweigtkettige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Alkoxylate eingesetzt werden können. Brauchbar sind demgemäß die Alkoxylate, insbesondere die Ethoxylate, primärer Alkohole mit linearen, insbesondere Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecyl-Resten sowie deren Gemische. Außerdem sind entsprechende Alkoxylierungsprodukte von Alkylaminen, vicinalen Diolen und Carbonsäureamiden, die hinsichtlich des Alkylteils den genannten Alkoholen entsprechen, verwendbar. Darüber hinaus kommen die Ethylenoxid- und/oder Propylenoxid-Insertionsprodukte von Fettsäurealkylestern sowie Fettsäurepolyhydroxyamiden in Betracht. Zur Einarbeitung in die erfindungsgemäßen Mittel geeignete sogenannte Alkylpolyglykoside sind Verbindungen der allgemeinen Formel (G)n-OR12, in der R12 einen Alkyl- oder Alkenylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und n eine Zahl zwischen 1 und 10 bedeuten. Bei der Glykosidkomponente (G)n handelt es sich um Oligo- oder Polymere aus natürlich vorkommenden Aldose- oder Ketose-Monomeren, zu denen insbesondere Glucose, Mannose, Fruktose, Galaktose, Talose, Gulose, Altrose, Allose, Idose, Ribose, Arabinose, Xylose und Lyxose gehören. Die aus derartigen glykosidisch verknüpften Monomeren bestehenden Oligomere werden außer durch die Art der in ihnen enthaltenen Zucker durch deren Anzahl, den sogenannten Oligomerisierungsgrad, charakterisiert. Der Oligomerisierungsgrad n nimmt als analytisch zu ermittelnde Größe im allgemeinen gebrochene Zahlenwerte an; er liegt bei Werten zwischen 1 und 10, bei den vorzugsweise eingesetzten Glykosiden unter einem Wert von 1,5, insbesondere zwischen 1,2 und 1,4. Bevorzugter Monomer-Baustein ist wegen der guten Verfügbarkeit Glucose. Der Alkyl- oder Alkenylteil R12 der Glykoside stammt bevorzugt ebenfalls aus leicht zugänglichen Derivaten nachwachsen der Rohstoffe, insbesondere aus Fettalkoholen, obwohl auch deren verzweigtkettige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Glykoside eingesetzt werden können. Brauchbar sind demgemäß insbesondere die primären Alkohole mit linearen Octyl-, Decyl-, Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Besonders bevorzugte Alkylglykoside enthalten einen Kokosfettalkylrest, das heißt Mischungen mit im wesentlichen R12=Dodecyl und R12=Tetradecyl.Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products come of fatty acid alkyl esters and Fettsäurepolyhydroxyamiden into consideration. So-called alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) n -OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. The glycoside component (G) n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R 12 of the glycosides preferably also originates from readily available derivatives of the raw materials, in particular fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used to prepare useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R 12 = dodecyl and R 12 = tetradecyl.
Als weitere fakultative tensidische Inhaltsstoffe kommen Seifen in Betracht, wobei gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure oder Stearinsäure, sowie aus natürlichen Fettsäuregemischen, zum Beispiel Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifen geeignet sind. Insbesondere sind solche Seifengemische bevorzugt, die zu 50 Gew.-% bis 100 Gew.-% aus gesättigten C12-C18-Fettsäureseifen und zu bis 50 Gew.-% aus Ölsäureseife zusammengesetzt sind. Vorzugsweise ist Seife in Mengen von 0,1 Gew.-% bis 5 Gew.-% enthalten. Insbesondere in flüssigen Mitteln, welche einen erfindungsgemäß verwendeten Wirkstoff enthalten, können jedoch auch höhere Seifenmengen von in der Regel bis zu 20 Gew.-% enthalten sein.Other optional surface-active ingredients are soaps, suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap. Preferably, soap is included in amounts of from 0.1% to 5% by weight. In particular, in liquid agents containing an active ingredient according to the invention, however, higher amounts of soap can be contained, usually up to 20 wt .-%.
Gewünschtenfalls können die Waschmittel auch Betaine und/oder kationische Tenside enthalten, die - falls vorhanden - vorzugsweise in Mengen von 0,5 Gew.-% bis 7 Gew.-% eingesetzt werden. Unter diesen sind Esterquats besonders bevorzugt.If desired, the detergents may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% to 7% by weight. Among these, esterquats are particularly preferred.
Die Waschmittel können gewünschtenfalls Bleichmittel auf Persauerstoffbasis, insbesondere in Mengen im Bereich von 5 Gew.-% bis 70 Gew.-%, sowie gegebenenfalls Bleichaktivator, insbesondere in Mengen im Bereich von 2 Gew.-% bis 10 Gew.-%, enthalten. Die in Betracht kommenden Bleichmittel sind vorzugsweise die in Waschmitteln in der Regel verwendeten Persauerstoffverbindungen wie Percarbonsäuren, beispielsweise Dodecandipersäure oder Phthaloylaminoperoxicapronsäure, Wasserstoffperoxid, Alkaliperborat, das als Tetra- oder Monohydrat vorliegen kann, Percarbonat, Perpyrophosphat und Persilikat, die in der Regel als Alkalisalze, insbesondere als Natriumsalze, vorliegen. Derartige Bleichmittel sind in Waschmitteln, welche einen erfindungsgemäß verwendeten Wirkstoff enthalten, vorzugsweise in Mengen bis zu 25 Gew.-%, insbesondere bis zu 15 Gew.-% und besonders bevorzugt von 5 Gew.-% bis 15 Gew.-%, jeweils bezogen auf gesamtes Mittel, vorhanden, wobei insbesondere Percarbonat zum Einsatz kommt. Die fakultativ vorhandene Komponente der Bleichaktivatoren umfasst die üblicherweise verwendeten N- oder O-Acylverbindungen, beispielsweise mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin, acylierte Glykolurile, insbesondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-isononanoyl-phenolsulfonat, und acylierte Zuckerderivate, insbesondere Pentaacetylglukose, sowie kationische Nitrilderivate wie Trimethylammoniumacetonitril-Salze. Die Bleichaktivatoren können zur Vermeidung der Wechselwirkung mit den Perverbindungen bei der Lagerung in bekannter Weise mit Hüllsubstanzen überzogen und/oder granuliert worden sein, wobei mit Hilfe von Carboxymethylcellulose granuliertes Tetraacetylethylendiamin mit mittleren Korngrößen von 0,01 mm bis 0,8 mm, granuliertes 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin, und/oder in Teilchenform konfektioniertes Trialkylammoniumacetonitril besonders bevorzugt ist. In Waschmitteln sind derartige Bleichaktivatoren vorzugsweise in Mengen bis zu 8 Gew.-%, insbesondere von 2 Gew.-% bis 6 Gew.-%, jeweils bezogen auf gesamtes Mittel, enthalten.If desired, the detergents may contain peroxygen bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, especially in amounts ranging from 2% to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents containing an active ingredient according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on total agent, present, in particular percarbonate is used. The optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. The bleach activators may have been coated and / or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or in particulate form, trialkylammonium acetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
In einer weiteren Ausführungsform enthält das Waschmittel wasserlöslichen und/oder wasserunlöslichen Builder, insbesondere ausgewählt aus Alkalialumosilikat, kristallinem Alkalisilikat mit Modul über 1, monomerem Polycarboxylat, polymerem Polycarboxylat und deren Mischungen, insbesondere in Mengen im Bereich von 2,5 Gew.-% bis 60 Gew.-%.In a further embodiment, the detergent contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.
Das Waschmittel enthält vorzugsweise 20 Gew.-% bis 55 Gew.-% wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasserlöslichen organischen Buildersubstanzen gehören insbesondere solche aus der Klasse der Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, sowie der polymeren (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden zugänglichen Polycarboxylate, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative Molekülmasse der Homopolymeren ungesättigter Carbonsäuren liegt im allgemeinen zwischen 5000 g/mol und 200000 g/mol, die der Copolymeren zwischen 2000 g/mol und 200000 g/mol, vorzugsweise 50000 g/mol bis 120000 g/mol, bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 50000 g/mol bis 100000 g/mol auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstsanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei Carbonsäuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/oder ein Vinylalkohol-Derivat oder ein Kohlenhydrat enthalten. Das erste saure Monomer oder dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-C8-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von (Meth-)acrylsäure ab. Das zweite saure Monomer oder dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure sein, wobei Maleinsäure besonders bevorzugt ist. Die dritte monomere Einheit wird in diesem Fall von Vinylalkohol und/oder vorzugsweise einem veresterten Vinylalkohol gebildet. Insbesondere sind Vinylalkohol-Derivate bevorzugt, welche einen Ester aus kurzkettigen Carbonsäuren, beispielsweise von C1-C4-Carbonsäuren, mit Vinylalkohol darstellen. Bevorzugte Terpolymere enthalten dabei 60 Gew.-% bis 95 Gew.-%, insbesondere 70 Gew.-% bis 90 Gew.-% (Meth)acrylsäure und/oder (Meth)acrylat, besonders bevorzugt Acrylsäure und/oder Acrylat, und Maleinsäure und/oder Maleinat sowie 5 Gew.-% bis 40 Gew.-%, vorzugsweise 10 Gew.-% bis 30 Gew.-% Vinylalkohol und/oder Vinylacetat. Ganz besonders bevorzugt sind dabei Terpolymere, in denen das Gewichtsverhältnis (Meth)acrylsäure und/oder (Meth)acrylat zu Maleinsäure und/oder Maleat zwischen 1:1 und 4:1, vorzugsweise zwischen 2:1 und 3:1 und insbesondere 2:1 und 2,5:1 liegt. Dabei sind sowohl die Mengen als auch die Gewichtsverhältnisse auf die Säuren bezogen. Das zweite saure Monomer oder dessen Salz kann auch ein Derivat einer Allylsulfonsäure sein, die in 2-Stellung mit einem Alkylrest, vorzugsweise mit einem C1-C4-Alkylrest, oder einem aromatischen Rest, der sich vorzugsweise von Benzol oder Benzol-Derivaten ableitet, substituiert ist. Bevorzugte Terpolymere enthalten dabei 40 Gew.-% bis 60 Gew.-%, insbesondere 45 bis 55 Gew.-% (Meth)acrylsäure und/oder (Meth)acrylat, besonders bevorzugt Acrylsäure und/oder Acrylat, 10 Gew.-% bis 30 Gew.-%, vorzugsweise 15 Gew.-% bis 25 Gew.-% Methallylsulfonsäure und/oder Methallylsulfonat und als drittes Monomer 15 Gew.-% bis 40 Gew.-%, vorzugsweise 20 Gew.-% bis 40 Gew.-% eines Kohlenhydrats. Dieses Kohlenhydrat kann dabei beispielsweise ein Mono-, Di-, Oligo- oder Polysaccharid sein, wobei Mono-, Di- oder Oligosaccharide bevorzugt sind, besonders bevorzugt ist Saccharose. Durch den Einsatz des dritten Monomers werden vermutlich Sollbruchstellen in dem Polymer eingebaut, die für die gute biologische Abbaubarkeit des Polymers verantwortlich sind. Diese Terpolymere weisen im Allgemeinen eine relative Molekülmasse zwischen 1000 g/mol und 200000 g/mol, vorzugsweise zwischen 2000 g/mol und 50000 g/mol und insbesondere zwischen 3000 g/mol und 10000 g/mol auf. Sie können, insbesondere zur Herstellung flüssiger Mittel, in Form wässriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wässriger Lösungen eingesetzt werden. Alle genannten Polycarbonsäuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt.The detergent preferably contains from 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of polycarboxylic acids, in particular citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also small proportions of polymerizable substances without carboxylic acid functionality may contain polymerized. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid , A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to 100,000 g / mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. It is also possible to use as water-soluble organic builder substances terpolymers which contain two carboxylic acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C 1 -C 4 carboxylic acids, with vinyl alcohol. Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid and / or (meth) acrylate to maleic acid and / or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2.5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt. % of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
Derartige organische Buildersubstanzen sind vorzugsweise in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und besonders bevorzugt von 1 Gew.-% bis 5 Gew.-% enthalten. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen, Mitteln eingesetzt.Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
Als wasserunlösliche, wasserdispergierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Alumosilikate in Waschmittelqualität, insbesondere Zeolith NaA und gegebenenfalls NaX, bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 µm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 µm. Ihr Calciumbindevermögen, das nach den Angaben der deutschen Patentschrift
Zusätzlich zum genannten anorganischen Builder können weitere wasserlösliche oder wasserunlösliche anorganische Substanzen in den Waschmitteln, welche einen erfindungsgemäß zu verwendenden Wirkstoff enthalten, mit diesem zusammen verwendet oder in erfindungsgemäßen Verfahren eingesetzt werden, enthalten sein. Geeignet sind in diesem Zusammenhang die Alkalicarbonate, Alkalihydrogencarbonate und Alkalisulfate sowie deren Gemische. Derartiges zusätzliches anorganisches Material kann in Mengen bis zu 70 Gew.-% vorhanden sein.In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the detergents which contain an active substance to be used according to the invention, used together with the latter or used in processes according to the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.
Zusätzlich können die Waschmittel weitere in Wasch- oder Reinigungsmitteln übliche Bestandteile enthalten. Zu diesen fakultativen Bestandteilen gehören insbesondere Enzyme, Enzymstabilisatoren, Komplexbildner für Schwermetalle, beispielsweise Aminopolycarbonsäuren, Aminohydroxypolycarbonsäuren, Polyphosphonsäuren und/oder Aminopolyphosphonsäuren, Schauminhibitoren, beispielsweise Organopolysiloxane oder Paraffine, Lösungsmittel und optische Aufheller, beispielsweise Stilbendisulfonsäurederivate. Vorzugsweise sind in Mitteln, welche einen erfindungsgemäß verwendeten Wirkstoff enthalten, bis zu 1 Gew.-%, insbesondere 0,01 Gew.-% bis 0,5 Gew.-% optische Aufheller, insbesondere Verbindungen aus der Klasse der substituierten 4,4'-Bis-(2,4,6-triamino-s-triazinyl)-stilben-2,2'-disulfonsäuren, bis zu 5 Gew.-%, insbesondere 0,1 Gew.-% bis 2 Gew.-% Komplexbildner für Schwermetalle, insbesondere Aminoalkylenphosphonsäuren und deren Salze und bis zu 2 Gew.-%, insbesondere 0,1 Gew.-% bis 1 Gew.-% Schauminhibitoren enthalten, wobei sich die genannten Gewichtsanteile jeweils auf gesamtes Mittel beziehen.In addition, the detergents may contain other usual in detergents or cleaning ingredients. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in agents which contain an active substance used according to the invention, up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular aminoalkylenephosphonic acids and their salts and up to 2% by weight, in particular 0.1% by weight contain up to 1 wt .-% foam inhibitors, wherein said weight fractions each refer to the total agent.
Die nicht-wässrigen Lösungsmittel, sind vorzugsweise solche nichtwässrigen Lösungsmittel, die wassermischbar sind. Zu diesen gehören die niederen Alkohole, beispielsweise Ethanol, Propanol, iso-Propanol, und die isomeren Butanole, Glycerin, niedere Glykole, beispielsweise Ethylen- und Propylenglykol, und die aus den genannten Verbindungsklassen ableitbaren Ether. In derartigen flüssigen Mitteln liegen die erfindungsgemäß verwendeten Wirkstoffe in der Regel gelöst oder in suspendierter Form vor.The nonaqueous solvents are preferably those nonaqueous solvents that are water miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. In such liquid agents, the active compounds used in the invention are usually dissolved or in suspended form.
Gegebenenfalls anwesende Enzyme werden vorzugsweise aus der Gruppe umfassend Protease, Amylase, Lipase, Cellulase, Hemicellulase, Oxidase, Peroxidase, Pektinase und Mischungen aus diesen ausgewählt. In erster Linie kommt aus Mikroorganismen, wie Bakterien oder Pilzen, gewonnene Protease in Frage. Sie kann in bekannter Weise durch Fermentationsprozesse aus geeigneten Mikroorganismen gewonnen werden. Proteasen sind im Handel beispielsweise unter den Namen BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® oder Maxapem® erhältlich. Die einsetzbare Lipase kann beispielsweise aus Humicola lanuginosa, aus Bacillus-Arten, aus Pseudomonas-Arten, aus Fusarium-Arten, aus Rhizopus-Arten oder aus Aspergillus-Arten gewonnen werden. Geeignete Lipasen sind beispielsweise unter den Namen Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase und Diosynth®-Lipase im Handel erhältlich. Geeignete Amylasen sind beispielsweise unter den Namen Maxamyl®, Termamyl®, Duramyl® und Purafect® OxAm handelsüblich. Die einsetzbare Cellulase kann ein aus Bakterien oder Pilzen gewinnbares Enzym sein, welches ein pH-Optimum vorzugsweise im schwach sauren bis schwach alkalischen Bereich von 6 bis 9,5 aufweist. Derartige Cellulasen sind unter den Namen Celluzyme®, Carezyme® und Ecostone® handelsüblich. Geeignete Pektinasen sind beispielsweise unter den Namen Gamanase®, Pektinex AR®, X-Pect® oder Pectaway® von Novozymes, unter dem Namen Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1L® von AB Enzymes und unter dem Namen Pyrolase® von Diversa Corp., San Diego, CA, USA erhältlich.Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®. Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
Zu den gegebenenfalls, insbesondere in flüssigen Waschmitteln vorhandenen üblichen Enzymstabilisatoren gehören Aminoalkohole, beispielsweise Mono-, Di-, Triethanol- und -propanolamin und deren Mischungen, niedere Carbonsäuren, Borsäure, Alkaliborate, Borsäure-Carbonsäure-Kombinationen, Borsäureester, Boronsäurederivate, Calciumsalze, beispielsweise Ca-Ameisensäure-Kombination, Magnesiumsalze, und/oder schwefelhaltige Reduktionsmittel.To the optionally present in particular liquid detergents usual enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.
Zu den geeigneten Schauminhibitoren gehören langkettige Seifen, insbesondere Behenseife, Fettsäureamide, Paraffine, Wachse, Mikrokristallinwachse, Organopolysiloxane und deren Gemische, die darüber hinaus mikrofeine, gegebenenfalls silanierte oder anderweitig hydrophobierte Kieselsäure enthalten können. Zum Einsatz in partikelförmigen Mitteln sind derartige Schauminhibitoren vorzugsweise an granulare, wasserlösliche Trägersubstanzen gebunden.Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.
Zu den bekanntlich polyesteraktiven schmutzablösevermögenden Polymeren, die zusätzlich zu den erfindungswesentlichen Wirkstoffen eingesetzt werden können, gehören Copolyester aus Dicarbonsäuren, beispielsweise Adipinsäure, Phthalsäure oder Terephthalsäure, Diolen, beispielsweise Ethylenglykol oder Propylenglykol, und Polydiolen, beispielsweise Polyethylenglykol oder Polypropylenglykol. Zu den bevorzugt eingesetzten schmutzablösevermögenden Polyestern gehören solche Verbindungen, die formal durch Veresterung zweier Monomerteile zugänglich sind, wobei das erste Monomer eine Dicarbonsäure HOOC-Ph-COOH und das zweite Monomer ein Diol HO-(CHR11-)aOH, das auch als polymeres Diol H-(O-(CHR11-)a)bOH vorliegen kann, ist. Darin bedeutet Ph einen o-, m- oder p-Phenylenrest, der 1 bis 4 Substituenten, ausgewählt aus Alkylresten mit 1 bis 22 C-Atomen, Sulfonsäuregruppen, Carboxylgruppen und deren Mischungen, tragen kann, R11 Wasserstoff, einen Alkylrest mit 1 bis 22 C-Atomen und deren Mischungen, a eine Zahl von 2 bis 6 und b eine Zahl von 1 bis 300. Vorzugsweise liegen in den aus diesen erhältlichen Polyestern sowohl Monomerdioleinheiten -O-(CHR11-)aO- als auch Polymerdioleinheiten -(O-(CHR11-)a)bO- vor. Das molare Verhältnis von Monomerdioleinheiten zu Polymerdioleinheiten beträgt vorzugsweise 100:1 bis 1:100, insbesondere 10:1 bis 1:10. In den Polymerdioleinheiten liegt der Polymerisationsgrad b vorzugsweise im Bereich von 4 bis 200, insbesondere von 12 bis 140. Das Molekulargewicht oder das mittlere Molekulargewicht oder das Maximum der Molekulargewichtsverteilung bevorzugter schmutzablöse-vermögender Polyester liegt im Bereich von 250 g/mol bis 100000 g/mol, insbesondere von 500 g/mol bis 50000 g/mol. Die dem Rest Ph zugrundeliegende Säure wird vorzugsweise aus Terephthalsäure, Isophthalsäure, Phthalsäure, Trimellithsäure, Mellithsäure, den Isomeren der Sulfophthalsäure, Sulfoisophthalsäure und Sulfoterephtalsäure sowie deren Gemischen ausgewählt. Sofern deren Säuregruppen nicht Teil der Esterbindungen im Polymer sind, liegen sie vorzugsweise in Salzform, insbesondere als Alkali- oder Ammoniumsalz vor. Unter diesen sind die Natrium- und Kaliumsalze besonders bevorzugt. Gewünschtenfalls können statt des Monomers HOOC-Ph-COOH geringe Anteile, insbesondere nicht mehr als 10 Mol-% bezogen auf den Anteil an Ph mit der oben gegebenen Bedeutung, anderer Säuren, die mindestens zwei Carboxylgruppen aufweisen, im schmutzablösevermögenden Polyester enthalten sein. Zu diesen gehören beispielsweise Alkylen- und Alkenylendicarbonsäuren wie Malonsäure, Bernsteinsäure, Fumarsäure, Maleinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure und Sebacinsäure. Zu den bevorzugten Diolen HO-(CHR11-)aOH gehören solche, in denen R11 Wasserstoff und a eine Zahl von 2 bis 6 ist, und solche, in denen a den Wert 2 aufweist und R11 unter Wasserstoff und den Alkylresten mit 1 bis 10, insbesondere 1 bis 3 C-Atomen ausgewählt wird. Unter den letztgenannten Diolen sind solche der Formel HO-CH2-CHR11-OH, in der R11 die obengenannte Bedeutung besitzt, besonders bevorzugt. Beispiele für Diolkomponenten sind Ethylenglykol, 1,2-Propylenglykol, 1,3-Propylenglykol, 1,4-Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, 1,8-Octandiol, 1,2-Decandiol, 1,2-Dodecandiol und Neopentylglykol. Besonders bevorzugt unter den polymeren Diolen ist Polyethylenglykol mit einer mittleren Molmasse im Bereich von 1000 g/mol bis 6000 g/mol.The known polyester-active soil release polymers which can be used in addition to the active compounds of the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R 11 denotes hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -O- (CHR 11 -) a O- and also polymeric diol units - ( O- (CHR 11 -) a ) b O-. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyesters is in the range of 250 g / mol to 100,000 g / mol , in particular from 500 g / mol to 50,000 g / mol. The acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol.
Gewünschtenfalls können diese wie oben beschrieben zusammengesetzten Polyester auch endgruppenverschlossen sein, wobei als Endgruppen Alkylgruppen mit 1 bis 22 C-Atomen und Ester von Monocarbonsäuren in Frage kommen. Den über Esterbindungen gebundenen Endgruppen können Alkyl-, Alkenyl- und Arylmonocarbonsäuren mit 5 bis 32 C-Atomen, insbesondere 5 bis 18 C-Atomen, zugrundeliegen. Zu diesen gehören Valeriansäure, Capronsäure, Önanthsäure, Caprylsäure, Pelargonsäure, Caprinsäure, Undecansäure, Undecensäure, Laurinsäure, Lauroleinsäure, Tridecansäure, Myristinsäure, Myristoleinsäure, Pentadecansäure, Palmitinsäure, Stearinsäure, Petroselinsäure, Petroselaidinsäure, Ölsäure, Linolsäure, Linolaidinsäure, Linolensäure, Eläostearinsäure, Arachinsäure, Gadoleinsäure, Arachidonsäure, Behensäure, Erucasäure, Brassidinsäure, Clupanodonsäure, Lignocerinsäure, Cerotinsäure, Melissinsäure, Benzoesäure, die 1 bis 5 Substituenten mit insgesamt bis zu 25 C-Atomen, insbesondere 1 bis 12 C-Atomen tragen kann, beispielsweise tert.-Butylbenzoesäure. Den Endgruppen können auch Hydroxymonocarbonsäuren mit 5 bis 22 C-Atomen zugrundeliegen, zu denen beispielsweise Hydroxyvaleriansäure, Hydroxycapronsäure, Ricinolsäure, deren Hydrierungsprodukt Hydroxystearinsäure sowie o-, m- und p-Hydroxybenzoesäure gehören. Die Hydroxymonocarbonsäuren können ihrerseits über ihre Hydroxylgruppe und ihre Carboxylgruppe miteinander verbunden sein und damit mehrfach in einer Endgruppe vorliegen. Vorzugsweise liegt die Anzahl der Hydroxymonocarbonsäureeinheiten pro Endgruppe, das heißt ihr Oligomerisierungsgrad, im Bereich von 1 bis 50, insbesondere von 1 bis 10. In einer bevorzugten Ausgestaltung der Erfindung werden Polymere aus Ethylenterephthalat und Polyethylenoxidterephthalat, in denen die Polyethylenglykol-Einheiten Molgewichte von 750 g/mol bis 5000 g/mol aufweisen und das Molverhältnis von Ethylenterephthalat zu Polyethylenoxidterephthalat 50:50 bis 90:10 beträgt, in Kombination mit einem erfindungswesentlichen Wirkstoff verwendet. Die schmutzablöse-vermögenden Polymere sind vorzugsweise wasserlöslich, wobei unter dem Begriff "wasserlöslich" eine Löslichkeit von mindestens 0,01 g, vorzugsweise mindestens 0,1 g des Polymers pro Liter Wasser bei Raumtemperatur und pH 8 verstanden werden soll. Bevorzugt eingesetzte Polymere weisen unter diesen Bedingungen jedoch eine Löslichkeit von mindestens 1 g pro Liter, insbesondere mindestens 10 g pro Liter auf.If desired, these polyesters composed as described above may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonsäuren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molar weights of 750 g / mole to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with an essential ingredient of the invention. The soil release polymers are preferably water-soluble, wherein the term "water-soluble" has a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water Room temperature and pH 8 should be understood. However, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.
Die Herstellung fester Waschmittel bietet keine Schwierigkeiten und kann auf bekannte Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Enzyme und eventuelle weitere thermisch empfindliche Inhaltsstoffe wie zum Beispiel Bleichmittel gegebenenfalls später separat zugesetzt werden. Zur Herstellung der Waschmittel mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/l bis 950 g/l, ist ein einen Extrusionschritt aufweisendes Verfahren bevorzugt.The preparation of solid detergents presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, with enzymes and any other thermally-sensitive ingredients such as, for example, bleaching agents optionally being added separately later. To produce the detergents with an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
In einer bevorzugten Ausführungsform enthält ein PEI-haltiges flüssiges Waschmittel 1 Gew.-% bis 15 Gew.-%, insbesondere 2 Gew.-% bis 10 Gew.-% nichtionisches Tensid, 2 Gew.-% bis 30 Gew.-%, insbesondere 5 Gew.-% bis 20 Gew.-% synthetisches Aniontensid, bis zu 15 Gew.-%, insbesondere 2 Gew.-% bis 12,5 Gew.-% Seife, 0,5 Gew.-% bis 5 Gew.-%, insbesondere 1 Gew.-% bis 4 Gew.-% organischen Builder, insbesondere Polycarboxylat wie Citrat, bis zu 1,5 Gew.-%, insbesondere 0,1 Gew.-% bis 1 Gew.-% Komplexbildner für Schwermetalle, wie Phosphonat, und neben gegebenenfalls enthaltenem Enzym, Enzymstabilisator, Farb- und/oder Duftstoff Wasser und/oder wassermischbares Lösungsmittel.In a preferred embodiment, a PEI-containing liquid detergent contains 1 wt .-% to 15 wt .-%, in particular 2 wt .-% to 10 wt .-% of nonionic surfactant, 2 wt .-% to 30 wt .-%, in particular from 5% by weight to 20% by weight of synthetic anionic surfactant, up to 15% by weight, in particular from 2% by weight to 12.5% by weight, of soap, from 0.5% by weight to 5% by weight. -%, In particular 1 wt .-% to 4 wt .-% organic builder, in particular polycarboxylate such as citrate, up to 1.5 wt .-%, in particular 0.1 wt .-% to 1 wt .-% complexing agent for heavy metals such as phosphonate, and optionally enzyme, enzyme stabilizer, color and / or perfume, water and / or water-miscible solvent.
In einer weiteren bevorzugten Ausführungsform ist das Waschmittel teilchenförmig und enthält bis zu 25 Gew.-%, insbesondere 5 Gew.-% bis 20 Gew.-% Bleichmittel, insbesondere Alkalipercarbonat, bis zu 15 Gew.-%, insbesondere 1 Gew.-% bis 10 Gew.-% Bleichaktivator, 20 Gew.-% bis 55 Gew.-% anorganischen Builder, bis zu 10 Gew.-%, insbesondere 2 Gew.-% bis 8 Gew.-% wasserlöslichen organischen Builder, 10 Gew.-% bis 25 Gew.-% synthetisches Aniontensid, 1 Gew.-% bis 5 Gew.-% nichtionisches Tensid und bis zu 25 Gew.-%, insbesondere 0,1 Gew.-% bis 25 Gew.-% anorganische Salze, insbesondere Alkalicarbonat und/oder - hydrogencarbonat.In a further preferred embodiment, the detergent is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, of up to 15% by weight, in particular 1% by weight. to 10% by weight of bleach activator, 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular 2% by weight to 8% by weight, of water-soluble organic builder, 10% by weight % to 25 wt .-% of synthetic anionic surfactant, 1 wt .-% to 5 wt .-% of nonionic surfactant and up to 25 wt .-%, in particular 0.1 wt .-% to 25 wt .-% of inorganic salts, in particular Alkali carbonate and / or bicarbonate.
Ein weiterer Aspekt der vorliegenden Erfindung umfasst ein Verfahren zum Reinigen eines verschmutzten textilen Substrats, wobei das Verfahren die Behandlung des feuchten Substrats mit der oben genannten Formulierung einschließt, die eine Vielzahl von wasserunlöslichen festen Polymerteilchen umfasst, bei dem die Polymerteilchen gegebenenfalls nach einer Regeneration mit oder ohne Einsatz des Waschmittels in weiteren Reinigungsverfahren gemäß dem Verfahren wiederverwendet werden.Another aspect of the present invention includes a method of cleaning a soiled textile substrate, the method including treating the wet substrate with the above formulation comprising a plurality of water-insoluble solid polymer particles, wherein the polymer particles are optionally regenerated with or be reused without the use of the detergent in further purification processes according to the method.
Das PEI enthaltende Waschmittel kann dabei vor dem Inkontaktbringen der Polymerteilchen mit dem verschmutzten textilen Substrat (Benetzung mit Wasser) während, vor oder nach dem Inkontaktbringen der Polymerteilchen mit dem Substrat in die Vorrichtung eingebracht werden. Selbstverständlich ist es auch möglich, das Waschmittel oder die wasserunlöslichen festen Teilchen in inkrementellen Schritten einzubringen.The PEI-containing detergent can be introduced into the device before the polymer particles are brought into contact with the soiled textile substrate (wetting with water) during, before or after contacting the polymer particles with the substrate. Of course, it is also possible to introduce the detergent or the water-insoluble solid particles in incremental steps.
Das zu reinigende Substrat umfasst erfindungsgemäß textile Substrate, jedes gegebenenfalls aus einer Vielzahl von Materialien, die entweder eine natürliche Faser, wie Baumwolle, oder synthetische Textilfasern, beispielsweise Nylon 6,6 oder ein Polyester sein können.The substrate to be cleaned according to the invention comprises textile substrates, each optionally of a variety of materials, which may be either a natural fiber such as cotton or synthetic textile fibers such as nylon 6,6 or a polyester.
Besonders bevorzugt als Polymerteilchen werden Polyalkene wie Polyethylen und Polypropylen, Polyester und Polyurethane. Bevorzugt werden jedoch die Polymerteilchen aus Polyamid, ganz besonders Teilchen aus Nylon, am meisten bevorzugt in der Form von Nylon-Chips. Die Polyamide sind besonders wirksam für wässrige Flecken/Schmutzentfernung, während Polyalkene besonders nützlich für die Entfernung von ölhaltigen Flecken sind. Gegebenenfalls können Copolymere der obigen polymeren Materialien für die Zwecke der Erfindung eingesetzt werden.Particularly preferred as polymer particles are polyalkenes such as polyethylene and polypropylene, polyesters and polyurethanes. However, preferred are the polymer particles of polyamide, more particularly particles of nylon, most preferably in the form of nylon chips. The polyamides are particularly effective for aqueous stain / soil removal, while polyalkenes are particularly useful for removing oily stains. Optionally, copolymers of the above polymeric materials may be used for the purposes of the invention.
Verschiedene Nylon Homo-oder Co-Polymere können verwendet werden, einschließlich Nylon 6 und Nylon 6,6. Vorzugsweise umfasst das Polyamid Nylon 6,6-Homopolymer mit einem mittleren Molekulargewicht im Bereich von 5.000 bis 30.000 Dalton, vorzugsweise 10.000 bis 20.000 Dalton, am meisten bevorzugt von 15.000 bis 16.000 Dalton.Various nylon homo- or co-polymers can be used, including nylon 6 and nylon 6,6. Preferably, the polyamide comprises nylon 6,6 homopolymer having an average molecular weight in the range of 5,000 to 30,000 daltons, preferably 10,000 to 20,000 daltons, most preferably 15,000 to 16,000 daltons.
Die wasserunlöslichen festen Teilchen beziehungsweise Granulat, Partikel oder Formkörper sind von einer solchen Form und Größe, die eine gute Fließfähigkeit und engen Kontakt mit dem textilen Substrat ermöglicht. Bevorzugte Formen der Teilchen schließen Kugeln und Würfel ein, aber die bevorzugte Teilchenform ist zylindrisch. Die Teilchen sind vorzugsweise so bemessen, dass sie jeweils ein Durchschnittsgewicht in dem Bereich von 20-50 mg, vorzugsweise 30-40 mg haben. Im Falle der am meisten bevorzugten zylindrisch geformten Teilchen beträgt der bevorzugte durchschnittliche Teilchendurchmesser 1,5 bis 6,0 mm, besonders bevorzugt 2,0 bis 5,0 mm, am meisten bevorzugt 2,5 bis 4,5 mm, während die Länge der zylindrischen Teilchen ist bevorzugt im Bereich von 2,0 bis 6,0 mm, besonders bevorzugt 3,0 bis 5,0 mm und am meisten bevorzugt im Bereich von 4,0 mm beträgt.The water-insoluble solid particles or granules, particles or moldings are of such a shape and size that enables good flowability and close contact with the textile substrate. Preferred forms of the particles include spheres and cubes, but the preferred particle shape is cylindrical. The particles are preferably sized to each have an average weight in the range of 20-50 mg, preferably 30-40 mg. In the case of the most preferred cylindrically shaped particles, the preferred average particle diameter is 1.5 to 6.0 mm, more preferably 2.0 to 5.0 mm, most preferably 2.5 to 4.5 mm, while the length of the cylindrical particles is preferably in the range of 2.0 to 6.0 mm, more preferably 3.0 to 5.0 mm, and most preferably in the range of 4.0 mm.
Vor der Reinigung wird das textile Substrat vorzugsweise durch Benetzen mit Wasser befeuchtet, um eine zusätzliche Verbesserung für die Waschflotte bereitzustellen und dadurch eine Verbesserung der Transporteigenschaften innerhalb des Systems zu ermöglichen (Vorbehandlung). Somit wird eine effizientere Übertragung von dem Waschmittel auf das Substrat und die Entfernung von Verschmutzungen und Flecken aus dem Substrat erleichtert. Am bequemsten kann das Substrat durch Kontakt mit Leitungswasser benetzt werden. Vorzugsweise wird die Benetzungsbehandlung durchgeführt, um ein Substrat zu Wasser-Gewichtsverhältnis von 1 : 0,1 bis 1 : 5 zu erreichen; mehr bevorzugt liegt das Verhältnis zwischen 1 : 0,2 und 1 : 2 liegt, wobei besonders günstige Ergebnisse mit in Verhältnissen wie 1 : 0,2, 1:1 und 1:2 erzielt werden. Jedoch können in einigen Fällen erfolgreiche Ergebnisse mit dem Substrat zu Wasser-Verhältnisse von bis 1 : 50 erreicht werden, obwohl solche Verhältnisse im Hinblick auf die erhebliche Mengen an Abwasser, die erzeugt werden, nicht bevorzugt sind.Prior to cleaning, the textile substrate is preferably moistened by wetting with water to provide additional enhancement to the wash liquor thereby allowing for an improvement in transport properties within the system (Pretreatment). Thus, more efficient transfer from the detergent to the substrate and the removal of soils and stains from the substrate is facilitated. Most conveniently, the substrate can be wetted by contact with tap water. Preferably, the wetting treatment is carried out to achieve a substrate to water weight ratio of 1: 0.1 to 1: 5; more preferably the ratio is between 1: 0.2 and 1: 2, with particularly favorable results being achieved in ratios such as 1: 0.2, 1: 1 and 1: 2. However, in some cases, successful results with the substrate can be achieved to water ratios of up to 1:50, although such ratios are not preferred in view of the significant amounts of wastewater that are generated.
Bei dem Verfahren gemäß diesem Aspekt der Erfindung, das als interstitielles Verfahren zwischen Reinigen und Scheuern angesehen werden kann, wird ein Gewichtsverhältnis von textilem Substrat zu wasserunlöslichen festen Teilchen im Bereich von 1:1 bis 1:30, insbesondere von 1:1,5 bis 1:2,5, ganz besonders von 1:2 eingestellt. Dabei wird der Anteil der wasserunlöslichen festen Teilchen als Gewicht der Teilchen im trockenen Zustand, d.h. nach 24-stündiger Lagerung bei 21°C und einer relativen Luftfeuchtigkeit von 65%, bestimmt.In the method according to this aspect of the invention, which can be regarded as an interstitial process between cleaning and scrubbing, a weight ratio of textile substrate to water-insoluble solid particles in the range of 1: 1 to 1:30, in particular from 1: 1.5 to 1: 2.5, especially set by 1: 2. The proportion of the water-insoluble solid particles as the weight of the particles in the dry state, i. after 24 hours storage at 21 ° C and a relative humidity of 65%.
Erfindungsgemäß können die wasserunlöslichen festen Teilchen vor dem Einsatz mit dem Waschmittel nach an sich bekannten Verfahren beschichtet werden.According to the invention, the water-insoluble solid particles can be coated prior to use with the detergent according to known methods.
Darüber hinaus hat es sich gezeigt, dass die Regenerierung der wasserunlöslichen festen Teilchen möglich ist, und die Teilchen in dem Reinigungsverfahren zufriedenstellend erneut verwendet werden, obwohl eine gewisse Verschlechterung in der Leistung im allgemeinen bei drei Verwendungen der Teilchen zu beobachten ist. Bei erneuter Verwendung der Teilchen werden optimale Ergebnisse erzielt, wenn diese erneut vor Wiedergebrauch mit dem Waschmittel beschichtet sind.In addition, it has been found that the regeneration of the water-insoluble solid particles is possible, and the particles are satisfactorily reused in the purification process, although some deterioration in performance is generally observed with three uses of the particles. Re-use of the particles will give optimum results when re-coated with the detergent before reuse.
Die Regenerierung der wasserunlöslichen festen Teilchen kann auf an sich bekannter Weise erfolgen, wie sie beispielsweise in der
Eine weitere Ausführungsform der Erfindung umfasst die Regenerierung der wasserunlöslichen, festen Polymerteilchen, wie in Anspruch 14 beschrieben.Another embodiment of the invention involves the regeneration of the water-insoluble, solid polymer particles as described in claim 14.
Eine weitere Ausführungsform der Erfindung umfasst die Verwendung einer Vielzahl von wasserunlöslichen festen Teilchen wie oben definiert, und ein PEI enthaltendes Waschmittel zur Reinigung von textilen Substraten durch Inkontaktbringen des Waschmittels und der Teilchen mit dem textilen Substrat wie im Anspruch 12 beschrieben.A further embodiment of the invention comprises the use of a plurality of water-insoluble solid particles as defined above, and a PEI-containing detergent for cleaning textile substrates by contacting the detergent and the particles with the textile substrate as described in claim 12.
Eine Vorrichtung zur Reinigung von verschmutzten textilen Substraten umfassend eine Vielzahl von wasserunlöslichen festen Teilchen, ein Reservoir zur Aufnahme der Teilchen innerhalb oder außerhalb der Vorrichtung und ein Waschmittel enthaltend polyalkoxylierte Polyamine wird auch offenbart.A device for cleaning soiled textile substrates comprising a plurality of water-insoluble solid particles, a reservoir for receiving the particles inside or outside the device, and a detergent containing polyalkoxylated polyamines is also disclosed.
Wesentliches Merkmal der Vorrichtung ist das Vorhandensein der obengenannten wasserunlöslichen festen Teilchen, ein Reservoir für die Teilchen und das polyalkoxylierte Polyamine enthaltende Waschmittel wie oben beschrieben.An essential feature of the device is the presence of the above water-insoluble solid particles, a reservoir for the particles and the polyalkoxylated polyamine-containing detergent as described above.
Die Vorrichtung weist typischerweise eine Klapptür in einem Gehäuse auf, um Zugang zum Inneren der Waschtrommel zu ermöglichen, um ein im Wesentlichen geschlossenes System bereitzustellen. Vorzugsweise schließt die Tür ein Fenster der stationären zylindrischen Trommel, die drehbar in einer weiteren Trommel gelagert ist, auf, während die drehbar gelagerte Zylindertrommel vertikal innerhalb des Gehäuses angebracht ist. Folglich wird eine Frontladeeinrichtung bevorzugt. Alternativ kann die stationäre zylindrische Trommel vertikal innerhalb des Gehäuses angebracht sein und die Zugriffseinrichtung sich in der Oberseite der Vorrichtung befinden.The apparatus typically includes a trap door in a housing to allow access to the interior of the washing tub to provide a substantially closed system. Preferably, the door includes a window of the stationary cylindrical drum rotatably supported in another drum while the rotatably supported cylinder drum is mounted vertically inside the housing. Consequently, a front loading device is preferred. Alternatively, the stationary cylindrical drum may be mounted vertically within the housing and the access device located in the top of the device.
Die Vorrichtung ist geeignet, um einen Kontakt der Teilchen mit dem verschmutzten Substrat bereitzustellen. Idealerweise sollten diese Teilchen wirksam zirkuliert werden, um eine effektive Reinigung zu fördern.The device is suitable for providing contact of the particles with the soiled substrate. Ideally, these particles should be efficiently circulated to promote effective purification.
Die Vorrichtung umfasst wenigstens ein Reservoir, insbesondere mit einer entsprechenden Steuerung, für die wasserunlöslichen festen Teilchen, das sich beispielsweise innerhalb der Waschmaschine befindet, die Teilchen zur Regenerierung beinhaltet und geeignet ist, den Fluss der Teilchen innerhalb der Waschmaschine zu steuern.The apparatus comprises at least one reservoir, in particular with a corresponding control, for the water-insoluble solid particles, for example located inside the washing machine, which contains particles for regeneration and is suitable for controlling the flow of particles within the washing machine.
In den Beispielen A bis H können folgende PEIs in den genannten Mengen einzeln oder in Kombination zum Einsatz kommen:
- PEI umgesetzt mit 45EO
- PEI umgesetzt mit 43EO
- PEI umgesetzt mit 15EO + 5PO
- PEI umgesetzt mit 15PO + 30EO
- PEI umgesetzt mit 5PO + 39,5EO
- PEI umgesetzt mit 5PO + 15EO
- PEI umgesetzt mit 10PO + 35EO
- PEI umgesetzt mit 15PO + 30EO
- PEI umgesetzt mit 15PO + 5EO
- PEI implemented with 45EO
- PEI implemented with 43EO
- PEI implemented with 15EO + 5PO
- PEI implemented with 15PO + 30EO
- PEI implemented with 5PO + 39.5EO
- PEI implemented with 5PO + 15EO
- PEI implemented with 10PO + 35EO
- PEI implemented with 15PO + 30EO
- PEI implemented with 15PO + 5EO
Claims (14)
- An aqueous washing liquor suitable for use in an apparatus for cleaning soiled textile substrates, containing a plurality of water-insoluble solid polymer particles and a liquid detergent containing polyalkoxylated polyamines and a non-aqueous solvent.
- The washing liquor according to claim 1, characterized in that the polyalkoxylated polyamines can be obtained by reacting polyamines with alkylene oxide, in particular ethylene oxide and/or propylene oxide.
- The washing liquor according to one of claims 1 to 2, characterized in that it comprises polyalkoxylated polyamines in combination with alkoxylated C8-C18 alcohols having an average degree of alkoxylation in the range of from 1 to 5.
- The washing liquor according to one of claims 1 to 3, characterized in that the polyalkoxylated polyamine has an average molar mass in the range of from 500 g/mol to 50,000 g/mol, in particular from 550 g/mol to 5,000 g/mol.
- The washing liquor according to one of claims 1 to 4, characterized in that 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 10 to 50.
- The washing liquor according to one of claims 1 to 5, characterized in that the average number of propoxy groups per primary or secondary amino function in the polyalkoxylated polyamine is from 1 to 40, in particular from 5 to 20, and the average number of ethoxy groups per primary or secondary amino function in the polyalkoxylated polyamine is from 10 to 60, in particular from 15 to 30.
- The washing liquor according to one of claims 1 to 6, characterized in that the terminal OH function of the polyalkoxy substituents in the polyalkoxylated polyamine can be partially or completely etherified with a C1-C10 alkyl group, in particular a C1-C3 alkyl group.
- The washing liquor according to one of claims 1 to 7, characterized in that the concentration of the polyalkoxylated polyamine in the liquid fraction of the washing liquor is from 1 mg/l to 500 mg/l, in particular from 5 mg/l to 100 mg/l.
- The washing liquor according to one of claims 1 to 8, characterized in that the polymer particles contain polyalkanes, polyesters, polyurethanes and/or polyamides including their copolymers, in particular a nylon 6.6 homopolymer having an average molar mass of from 5,000 to 30,000 daltons.
- The washing liquor according to one of claims 1 to 9, characterized in that the water-insoluble solid particles are in the form of spheres, cubes and/or cylinders.
- The washing liquor according to one of claims 1 to 10, characterized in that each of the water-insoluble solid particles has an average weight in the range of from 20 to 50 mg.
- The use of a plurality of water-insoluble solid polymer particles and of a liquid detergent containing polyalkoxylated polyamines and a non-aqueous solvent for cleaning soiled textile substrates, in particular textile substrates having oil- and/or fat-containing, protein-containing and/or fruit-containing stains, by bringing the detergent and the polymer particles into contact with the textile substrate.
- A method for cleaning soiled textile substrates using a washing liquor according to one of claims 1 to 11.
- The regeneration of a plurality of soiled water-insoluble solid polymer particles as defined in one of claims 1 to 11 using a washing liquor, as defined in one of claims 1 to 11, by bringing the polymer particles into contact with the liquid detergent containing the polyalkoxylated polyamines and a non-aqueous solvent.
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DE102014213315.7A DE102014213315A1 (en) | 2014-07-09 | 2014-07-09 | Polyalkoxylated polyamines in novel washing processes |
PCT/EP2015/065625 WO2016005461A1 (en) | 2014-07-09 | 2015-07-08 | Polyalkoxylated polyamines in novel laundry methods |
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US10731108B2 (en) | 2017-12-01 | 2020-08-04 | The Procter & Gamble Cincinnati | Processes of making liquid detergent compositions that include zwitterionic surfactant |
US20190169551A1 (en) * | 2017-12-01 | 2019-06-06 | The Procter & Gamble Company | Processes of making liquid detergent compositions that include certain alkoxylated pei polymers |
EP4157918B1 (en) | 2020-05-29 | 2024-04-10 | Basf Se | Amphoterically-modified oligopropyleneimine ethoxylates for improved stain removal of laundry detergents |
JP2023529990A (en) | 2020-06-17 | 2023-07-12 | ビーエーエスエフ ソシエタス・ヨーロピア | Amphiphilic Alkoxylated Polyethylene/-Propyleneimine Copolymers for Multi-Benefit Detergent Formulations |
WO2023094275A1 (en) | 2021-11-29 | 2023-06-01 | Basf Se | Amphoterically-modified trialkylene tetramine ethoxylates for improved stain removal of laundry detergents |
WO2023117494A1 (en) | 2021-12-20 | 2023-06-29 | Basf Se | Polypropylene imine polymers (ppi), their preparation, uses, and compositions comprising such ppi |
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