EP3036315B1 - Produits de lavage et de nettoyage à efficacité améliorée - Google Patents

Produits de lavage et de nettoyage à efficacité améliorée Download PDF

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EP3036315B1
EP3036315B1 EP14750766.9A EP14750766A EP3036315B1 EP 3036315 B1 EP3036315 B1 EP 3036315B1 EP 14750766 A EP14750766 A EP 14750766A EP 3036315 B1 EP3036315 B1 EP 3036315B1
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acid
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detergents
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EP3036315A1 (fr
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Inga Kerstin Vockenroth
Eva-Maria Wikker
Sylvia Aust
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the present invention relates to the use of polyalkoxylated polyamines in detergents and cleaning agents to improve washing or cleaning performance.
  • the complicating factor is that instead of removing the so-called bleachable soiling, which is normally at least partially removed by the peroxygen-based bleaching agent, the washing process often, on the contrary, actually causes an intensification and/or deterioration in the removal of the soiling, which is not the case Ultimately, this can be attributed to initiated chemical reactions, which can consist, for example, in the polymerization of certain dyes contained in the stains.
  • the polymerizable substances are primarily polyphenolic dyes, preferably flavonoids, in particular from the class of anthocyanidins or anthocyanins.
  • the stains may have been caused in particular by food products or drinks that contain corresponding dyes.
  • the stains can in particular be stains from fruits or vegetables or even red wine stains, which in particular contain polyphenolic dyes, especially those from the class of anthocyanidins or anthocyanins.
  • Alkoxylated polyamines and their use in detergents and cleaning agents are, for example, from international patent applications WO 95/32272 A1 and WO 2006/108857 A1 known.
  • a first object of the present invention is therefore the use of a combination of polyalkoxylated polyamine and polyacrylate in a weight ratio in the range from 3:1 to 1:3 in detergents or cleaning agents to improve the washing or cleaning performance against bleachable stains and against protein-containing stains.
  • the invention thus leads to an overall improved washing and cleaning result if bleachable soils and protein-containing soils are to be removed at the same time in a washing or cleaning process.
  • “Bleachable stains” should be understood to mean those that show at least partial lightening when exposed to oxidizing agents such as H 2 O 2 , alkali metal percarbonate or alkali metal perborate, even if they are not always completely removed from the textile in conventional washing processes using a detergent containing bleach.
  • the bleachable soils usually contain polymerizable substances, in particular polymerizable dyes, the polymerizable dyes preferably being polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds.
  • soiling in the colors green, yellow, red or blue it is also possible to remove soiling in intermediate colors, in particular violet, purple, brown, purple or pink, and also soiling that has a green, yellow, red, violet color , mauve, brown, purple, pink or blue tint without essentially consisting entirely of that color.
  • the colors mentioned can in particular also be light or dark.
  • This is preferably soiling, in particular stains from grass, fruits or vegetables, and in particular soiling from food products, such as spices, sauces, chutneys, curries, purees and jams, or drinks, such as coffee, tea, wines and so on Juices containing appropriate green, yellow, red, violet, lilac, brown, purple, pink and/or blue dyes.
  • Protein-containing soils are to be understood as meaning those which, when exposed to protease, possibly in collaboration with lipase, amylase, mannanase and/or pectinase, show at least partial removal or lightening, even if they are normal Washing processes using a detergent containing enzymes cannot always be completely removed from the textile.
  • the soiling to be removed according to the invention can in particular be caused by cherries, morello, grapes, apples, pomegranates, aronia, plums, sea buckthorn, açai, kiwi, mango, grass, or berries, especially red or black currants, elderberries, blackberries, raspberries , blueberries, cranberries, cranberries, strawberries or blueberries, through coffee, tea, red cabbage, blood orange, eggplant, tomato, carrot, beetroot, spinach, pepper, red-fleshed or blue-fleshed potato, red onion, milk, egg, chocolate, cocoa, blood , grass, salad dressing and mixtures of the above, such as those found in foods such as chocolate milk, jams or pudding.
  • the polyalkoxylated polyamine is a polymer with a backbone containing N atoms and carrying 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 necessary, it can also only have secondary amino functions inside, so that the result is not a branched-chain, but a linear polyamine.
  • the ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1:0.5 to 1:1.5, in particular in the range from 1:0.7 to 1:1.
  • the ratio of primary to tertiary amino groups in the polyamine is preferably in the range from 1:0.2 to 1:1, in particular in the range from 1:0.5 to 1:0.8.
  • the polyamine preferably has an average molecular weight in the range from 500 g/mol to 50,000 g/mol, in particular from 550 g/mol to 2000 g/mol.
  • the average molecular weights given here and later for other polymers are weight-average molecular weights M w , which can generally be determined using gel permeation chromatography with the aid of an RI detector, the measurement expediently being carried out against an external standard.
  • the N atoms in the polyamine are preferably separated from one another by alkylene groups with 2 to 12 carbon atoms, in particular 2 to 6 carbon atoms, although not all alkylene groups have to have the same number of carbon atoms.
  • Ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof are particularly preferred.
  • the primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions can carry 1 polyalkoxy group, although not every amino function has to be alkoxy group-substituted.
  • the average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 5 to 100, in particular 10 to 80.
  • the alkoxy groups in the polyalkoxylated polyamine are preferably ethoxy, propoxy or butoxy groups or mixtures of these, in particular ethoxy groups ; According to the invention, the alkoxy groups particularly preferably consist exclusively of ethoxy groups.
  • the polyalkoxylated polyamines are accessible by reacting the polyamines with epoxides corresponding to the alkoxy groups.
  • the terminal OH function can at least some of the polyalkoxy substituents can be replaced by an alkyl ether function with 1 to 10, in particular 1 to 3, carbon atoms.
  • the polyacrylate is an alkali metal or ammonium salt of a polymer obtainable by radical polymerization of acrylic acid and/or methacrylic acid. Sodium, potassium, ammonium, mono-, di-, tri- and tetraalkyl ammonium salts and mixtures of these are preferred, with each of the alkyl groups located on the N atom of the ammonium unit also carrying an OH substituent can, and preferably has 1 to 3 carbon atoms.
  • the polyacrylate preferably has an average molecular weight in the range from 1000 g/mol to 20,000 g/mol, in particular from 1500 g/mol to 15,000 g/mol.
  • the polymer can, in addition to the proportions originating from acrylic acid and/or methacrylic acid, also contain minor proportions, in particular not more than 30 mol%, of proportions originating from other ethylenically unsaturated monomers.
  • the acid group-containing monomers mentioned can also be present in the form of their salts, in particular their alkali metal salts.
  • the use according to the invention of the combination of polyalkoxylated polyamine and polyacrylate in detergents or cleaning agents is preferably carried out by adding them in an amount of 0.1% by weight to 5% by weight, in particular in an amount of 1% by weight. up to 3% by weight, whereby the “% by weight” information here and below refers to the weight of the entire detergent or cleaning agent.
  • the combination to be used according to the invention preferably contains polyalkoxylated polyamine and polyacrylate in a weight ratio in the range from 2:1 to 1:2.
  • the detergent or cleaning agent can be present in any dosage form established according to the state of the art and/or any convenient dosage form. These include, for example, solid, powdery, liquid, gel or pasty dosage forms, possibly also consisting of several phases; This also includes, for example: extrudates, granules, tablets or pouches, both in large containers and packaged in portions.
  • the use according to the invention takes place in a detergent and cleaning agent that does not contain any bleaching agents.
  • the agent does not contain bleaching agents in the narrower sense, i.e. hypochlorites, hydrogen peroxide or hydrogen peroxide delivering substances, contains; preferably it also has no bleach activators and/or bleach catalysts.
  • the detergent is a liquid textile detergent.
  • the detergent is a powdered or liquid color detergent, i.e. a textile detergent for colored textiles.
  • the detergents and cleaning agents can also contain common other components of detergents or cleaning agents, in particular textile detergents, in particular selected from the group of builders, surfactants, polymers, disintegration aids, fragrances and perfume carriers.
  • the builders include in particular zeolites, silicates, carbonates, organic cobuilders and - provided there are no ecological prejudices against their use - also phosphates.
  • the finely crystalline, synthetic zeolite containing bound water is preferably zeolite A and/or zeolite P.
  • Zeolite MAP® commercial product from Crosfield
  • zeolite X and mixtures of zeolite A, which is given by the formula n NazO ⁇ (1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2 - 2.5) SiOz ⁇ (3.5 - 5.5) H 2 O can be described.
  • the zeolite can be used both as a builder in a granular compound and as a kind of "powdering" of a granular mixture, preferably a mixture to be pressed, with both ways of incorporating the zeolite into the premix usually being used.
  • Zeolites can have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18% by weight to 22% by weight, in particular 20% by weight to 22% by weight, of bound water.
  • Crystalline layered silicates of the general formula NaMSi x O 2x + 1 ⁇ y H 2 O can also be used, in which M represents sodium or hydrogen, particularly preferred values for x are 2, 3 or 4, and y for is a number from 0 to 33, preferably from 0 to 20.
  • the crystalline layered silicates of the formula NaMSi x O 2x+1 ⁇ y H 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 ⁇ x HzO, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ⁇ x HzO, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 ⁇ x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ x H 2 O, Makatite).
  • Crystalline layered silicates of the formula NaMSi x O 2x+1 ⁇ y HzO, in which x is 2, are preferred.
  • both ⁇ - and 5-sodium disilicates are Na 2 Si 2 O 5 ⁇ y H 2 O and, above all, Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 (ß-Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 ⁇ H 2 O), Na-SKS-10 (NaHSi 2 O 5 ⁇ 3 HzO, kanemite), Na-SKS-11 (t- Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ) are preferred.
  • Detergents or cleaning agents preferably contain a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x+1 ⁇ y H 2 O of 0.1% by weight to 20% by weight, preferably from 0.2% by weight to 15% by weight and in particular from 0.4% by weight to 10% by weight.
  • Amorphous sodium silicates with a modulus NazO:SiOz of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which are preferably delayed in dissolution, can also be used and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction/densification or by overdrying.
  • the term "amorphous" means that the silicates in X-ray diffraction experiments do not produce sharp X-ray reflections, as are typical for crystalline substances, but at most produce one or more maxima of the scattered X-radiation, which have a width of several degree units of the diffraction angle.
  • X-ray amorphous silicates can be used, the silicate particles of which produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas with a size of ten to several hundred nm, with values up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred.
  • Such X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Particularly preferred are densified/compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • silicate(s) preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, are, if present, in detergents or cleaning agents in amounts of 3% by weight to 60% by weight, preferably 8% by weight. % to 50% by weight and in particular from 20% by weight to 40% by weight.
  • alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can differentiate between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 alongside higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to cleaning performance.
  • Technically particularly important phosphates are pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • Sodium potassium tripolyphosphates are also preferably used.
  • phosphates are used in detergents or cleaning agents
  • preferred agents contain these phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5% by weight. % to 80% by weight, preferably from 15% by weight to 75% by weight and in particular from 20% by weight to 70% by weight.
  • Alkaline carriers can also be used.
  • Alkaline carriers include, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, the above-mentioned alkali metal silicates, alkali metasilicates, and mixtures of the aforementioned substances, with preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate can be particularly preferred.
  • the alkali metal hydroxides are usually only used in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 % by weight and in particular below 2% by weight. Particular preference is given to agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides. It is preferred to use carbonate(s) and/or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of from 2% by weight to 50% by weight, preferably from 5% by weight to 40% by weight and in particular from 7.5% by weight to 30% by weight.
  • polycarboxylates/polycarboxylic acids Particular organic builders that should be mentioned are polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and phosphonates.
  • polycarboxylic acids that can be used in the form of the free acid and/or their sodium salts are useful
  • Polycarboxylic acids are those carboxylic acids that carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures of these.
  • the free acids typically also have the property of an acidifying component and are therefore also used to adjust a lower and milder pH value of detergents or cleaning agents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned.
  • Polymeric aminodicarboxylic acids, their salts or their precursor substances should also be mentioned as further preferred builder substances. Polyaspartic acids and/or their salts are particularly preferred.
  • phosphonates are the salts of, in particular, hydroxyalkane or aminoalkane phosphonic acids.
  • hydroxyalkanephosphonic acids 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance. It is used in particular as a sodium salt, with the disodium salt reacting neutrally and the tetrasodium salt reacting alkaline.
  • Particularly suitable aminoalkanephosphonic acids are ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologues.
  • polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and/or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out using conventional processes, for example acid- or enzyme-catalyzed processes. These are preferably hydrolysis products with average molecular weights in the range from 400 g/mol to 500,000 g/mol.
  • DE dextrose equivalent
  • Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins can be used and white dextrins with higher molecular weights in the range of 2000 g/mol to 30000 g/mol.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Ethylenediamine N,N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerin disuccinates and glycerol trisuccinates are also preferred in this context. If desired, suitable use amounts are 3% by weight to 15% by weight, particularly in zeolite-containing and/or silicate-containing formulations.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which can optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups.
  • Detergents and cleaning agents can contain nonionic, anionic, cationic and/or amphoteric surfactants.
  • nonionic surfactants known to those skilled in the art can be used as nonionic surfactants.
  • Detergents or cleaning agents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the ethoxylation levels reported represent statistical averages, which may correspond to a whole or a fractional number for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO( G ) G is the symbol that stands for a glycose unit with 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be used.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula, in which R represents an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 represents hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances that can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula in which R represents a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, where C 1-4 alkyl or phenyl radicals are preferred and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
  • nonionic surfactants are from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO/AO/EO nonionic surfactants, or the PO/AO/PO nonionic surfactants, especially PO/EO/ PO nonionic surfactants are particularly preferred.
  • Such PO/EO/PO nonionic surfactants are characterized by good foam control.
  • the anionic surfactants used are, for example, those of the sulfonate and sulfate types.
  • Sulfonate-type surfactants are preferably C 9-13 alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is taken into consideration.
  • Alkane sulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable.
  • the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triester and mixtures thereof, such as those obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk(en)yl sulfates are the alkali metal and in particular the sodium salts of the sulfuric acid monoesters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, Cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk(en)yl sulfates of the chain length mentioned, which contain a synthetic straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on fatty chemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which can be obtained as commercial products from the Shell Oil Company under the name DAN® , are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming properties, they are only used in cleaning agents in relatively small amounts, for example in amounts of 1% by weight to 5% by weight.
  • Suitable anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters and which represent monoesters and/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 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves represent nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk(en)yl succinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or its salts.
  • Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids, are suitable.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Cationic and/or amphoteric surfactants can also be used instead of the surfactants mentioned or in conjunction with them.
  • Textile-softening compounds can be used to care for the textiles and to improve the textile properties such as a softer “handle” (avivage) and reduced electrostatic charge (increased wearing comfort).
  • the active ingredients of these formulations are quaternary ammonium compounds with two hydrophobic residues, such as disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
  • esters with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and/or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents.
  • Dimethylolethylene urea is also suitable as a finish.
  • the enzymes that can optionally be used in detergents or cleaning agents include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents and are therefore preferred.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 % by weight to 5% by weight based on active protein.
  • the protein concentration can be determined using known methods, for example the BCA method or the Biuret method.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN' and Carlsberg and their further developed forms the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, which can be assigned to the subtilases but no longer to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the aforementioned amylases that have been improved for use in detergents and cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) should be highlighted.
  • Lipases or cutinases can be used because of their triglyceride-splitting activity. These include, for example, the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus) or further developed from them, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can be used. Lipases and/or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.
  • Humicola lanuginosa Thermomyces lanuginosus
  • Lipases and/or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect.
  • organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to strengthen the activity of the relevant oxidoreductases (enhancers) or in the case of very different ones Redox potentials between the oxidizing enzymes and the contaminants ensure the flow of electrons (mediators).
  • the enzymes can be used in any form established in the state of the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or containing stabilizers.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is covered with a protective layer impermeable to water, air and/or chemicals.
  • Additional active ingredients such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes.
  • Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.
  • One or more enzymes and/or enzyme preparations are preferred in amounts of 0.1% by weight to 5% by weight, preferably from 0.2% by weight to 4 .5% by weight and in particular from 0.4% by weight to 4% by weight.
  • fragrance compounds for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. However, mixtures of different fragrances are preferably used, which together produce an appealing scent. Such perfume oils can also contain natural fragrance mixtures such as those available from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. In order to be perceivable, a fragrance must be volatile; in addition to the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. Most fragrances have molecular weights of up to around 200 g/mol, while molecular weights of 300 g/mol and above are rather an exception.
  • the smell of a perfume or fragrance composed of several fragrances changes during evaporation, with the odor impressions being divided into “top note” and “middle note” or “body”. ) and “base note” (end note or dry out). Since the perception of smell is largely based on the intensity of the smell, the top note consists of one Perfume or fragrance does not only consist of volatile compounds, while the base note consists largely of less volatile, ie more adhesive, fragrances. When composing perfumes, more volatile fragrances can, for example, be bound to certain fixatives, which prevents them from evaporating too quickly.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers, which ensure a long-lasting scent through a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can also be coated with other auxiliary substances.
  • the colorants When choosing the colorant that may be present, it must be taken into account that the colorants have a high storage stability and are insensitive to light as well as not having a strong affinity for textile surfaces and in particular for synthetic fibers. At the same time, it must also be taken into account that colorants can have different levels of stability towards oxidation. In general, water-insoluble dyes are more stable to oxidation than water-soluble dyes. Depending on the solubility and therefore also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaning agents varies. For dyes that are readily water-soluble, dye concentrations in the range from a few 10 -2 % by weight to 10 -3 % by weight are typically selected.
  • the suitable concentration of the colorant in detergents or cleaning agents is typically a few 10 -3 % by weight to 10 -4 % by weight. Colorants that can be destroyed oxidatively in the washing process are preferred, as well as mixtures of these with suitable blue dyes, so-called blue tinters. It has proven to be advantageous to use colorants that are soluble in water or in liquid organic substances at room temperature.
  • anionic dyes for example anionic nitroso dyes, are suitable.
  • the detergents or cleaning agents can contain further ingredients which further improve the application-related and/or aesthetic properties of these agents.
  • Preferred agents contain one or more substances from the group of electrolytes, pH adjusters, fluorescent agents, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, shrink preventers, anti-crease agents, color transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, antistatic agents, ironing aids , phobic and impregnating agents, swelling and anti-slip agents as well as UV absorbers.
  • a wide range of different salts can be used as electrolytes from the group of inorganic salts.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing perspective, the use of NaCl or MgCl 2 in the detergents or cleaning agents is preferred.
  • pH adjusters may be advisable. All known acids or alkalis can be used here, provided their use is not prohibited for application-related or ecological reasons or for consumer protection reasons.
  • the amount of these adjusting agents usually does not exceed 1% by weight of the total formulation.
  • Suitable foam inhibitors include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable carrier materials include, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials.
  • Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and/or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R 2 SiO) x and are also referred to as silicone oils.
  • silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000 g/mol and 150,000 g/mol and viscosities between 10 mPa s and 1000,000 mPa s.
  • Suitable soil repellents are the polymers of phthalic acid and/or terephthalic acid and their derivatives known from the prior art, in particular polymers of ethylene terephthalate and/or polyethylene glycol terephthalate or anionically and/or nonionically modified derivatives of these.
  • the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.
  • Optical brighteners can be added to detergents in particular to eliminate graying and yellowing of the treated textiles. These substances absorb onto the fiber and cause a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, with the ultraviolet light absorbed from sunlight being emitted as a weak bluish fluorescence and pure with the yellow tone of the grayed or yellowed laundry White results.
  • Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbendisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalamides, benzoxazole. , benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.
  • the task of graying inhibitors is to keep the dirt that has been detached from the fiber suspended in the liquor and thus prevent the dirt from being absorbed again.
  • Water-soluble colloids usually of an organic nature, are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Use soluble starch preparations e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxy-methylcellulose and mixtures thereof can also be used as graying inhibitors.
  • synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • Phobia and impregnation processes are used to equip textiles with substances that prevent dirt from depositing or make it easier to wash out.
  • Preferred repelling and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with a perfluorinated alcohol component or polymerizable compounds coupled with a perfluorinated acyl or sulfonyl radical.
  • Antistatic agents may also be included.
  • the dirt-repellent finish with repellents and waterproofing agents is often classified as easy-care finish.
  • the penetration of the impregnating agents in the form of solutions or emulsions of the active ingredients in question can be facilitated by adding wetting agents which reduce the surface tension.
  • hydrophobic agents used for hydrophobicization cover textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable hydrophobic agents include paraffins, waxes, metal soaps, etc.
  • silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juice and the like are easier to remove.
  • Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between: Bacteriostatics and bactericides, fungistatics and fungicides, etc. Substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenphenols and phenolmercuriacetate, although these compounds can also be dispensed with entirely.
  • the agents can contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase surface conductivity and thus enable improved discharge of charges that have formed.
  • External antistatic agents are usually substances with at least one hydrophilic molecular ligand and produce a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, which also achieves a finishing effect.
  • silicone derivatives can be used in textile detergents. These also improve the rinsing behavior of detergents or cleaning agents thanks to their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are wholly or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and/or Si-Cl bonds.
  • silicones are the polyalkylene oxide-modified polysiloxanes, i.e. polysiloxanes which have, for example, polyethylene glycols, and the polyalkylene oxide-modified dimethylpolysiloxanes.
  • UV absorbers can also be used, which absorb onto the treated textiles and improve the light resistance of the fibers.
  • Compounds that have these desired properties are, for example, the compounds and derivatives of benzophenone with substituents in the 2- and/or 4-position that are effective through radiationless deactivation.
  • Substituted benzotriazoles, acrylates substituted with phenyl in the 3-position (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid are also suitable.
  • Protein hydrolysates are further suitable active substances due to their fiber-care effect. Protein hydrolysates are product mixtures that are obtained through acidic, basic or enzymatically catalyzed degradation of proteins. Protein hydrolysates of both plant and animal origin can be used. Animal protein hydrolysates include, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which can also be in the form of salts. The use of protein hydrolysates of plant origin, for example soy, almond, rice, pea, potato and wheat protein hydrolysates, is preferred.
  • protein hydrolysates as such is preferred, amino acid mixtures obtained elsewhere or individual amino acids such as, for example, arginine, lysine, histidine or pyroglutamic acid can also be used instead. It is also possible to use derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.

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

Claims (10)

  1. Utilisation d'une combinaison de polyamine polyalcoxylée et de polyacrylate dans un rapport pondéral dans la plage de 3:1 à 1:3 dans des produits de lavage ou de nettoyage pour améliorer la performance de lavage ou de nettoyage vis-à-vis de salissures pouvant être blanchies et vis-à-vis de salissures contenant des protéines.
  2. Utilisation selon la revendication 1, caractérisée en ce que les souillures contiennent des substances polymérisables choisies parmi les colorants polyphénoliques, en particulier les flavono des, notamment les colorants de la classe des anthocyanidines ou des anthocyanes ou des oligomères de ces composés, et des protéines.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les souillures sont choisies parmi les souillures par la cerise, la morelle, le raisin, la pomme, la grenade, l'aronia, la prune, l'argousier, l'açai, le kiwi, la mangue, l'herbe, ou les baies, notamment les groseilles rouges ou noires, les baies de sureau, les mûres, framboises, myrtilles, airelles rouges, baies de coronaire, fraises ou myrtilles, par le café, le thé, le chou rouge, l'orange sanguine, l'aubergine, la tomate, la carotte, la betterave rouge, les épinards, le poivron, la pomme de terre à chair rouge ou à chair bleue, l'oignon rouge, le lait, l'œuf, le chocolat, le cacao, le sang, l'herbe, la vinaigrette et les mélanges de ceux-ci.
  4. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que la polyamine présente une masse molaire moyenne comprise entre 500 g/mol et 50 000 g/mol, en particulier entre 550 g/mol et 2000 g/mol.
  5. Utilisation selon l'une des revendications 1 à 4, caractérisée en ce que les atomes d'azote dans la polyamine sont séparés les uns des autres par des groupes alkylène ayant de 2 à 12 atomes de carbone, en particulier de 2 à 6 atomes de carbone, tous les groupes alkylène n'ayant pas nécessairement le même nombre d'atomes de carbone.
  6. Utilisation selon l'une quelconque des revendications 1 à 5, caractérisée en ce que le nombre moyen de groupes alcoxy par fonction amine primaire et secondaire dans la polyamine polyalcoxylée est de 5 à 100, en particulier de 10 à 80.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que les groupes alcoxy dans la polyamine polyalcoxylée sont des groupes éthoxy, propoxy ou butoxy ou des mélanges de ceux-ci, en particulier des groupes éthoxy.
  8. Utilisation selon l'une des revendications 1 à 7, caractérisée en ce que le polyacrylate présente une masse molaire moyenne comprise entre 1000 g/mol et 20000 g/mol, en particulier entre 1500 g/mol et 15000 g/mol.
  9. Utilisation selon l'une quelconque des revendications 1 à 8, caractérisée en ce que, dans la combinaison, de la polyamine polyalcoxylée et du polyacrylate sont présents dans un rapport pondéral dans la plage de 2:1 à 1:2.
  10. Utilisation selon l'une des revendications 1 à 9, caractérisée en ce qu'on utilise la combinaison de polyamine polyalcoxylée et de polyacrylate dans des produits de lavage ou de nettoyage en une quantité de 0,1 % en poids à 5 % en poids, en particulier en une quantité de 1 % en poids à 3 % en poids.
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CA2494131C (fr) * 2002-09-12 2013-03-19 The Procter & Gamble Company Solutions de polymeres et produits de nettoyage contenant celles-ci
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MX2008016448A (es) * 2006-06-19 2009-01-22 Procter & Gamble Composiciones detergentes liquidas con polimeros a base de acido poliacrilico y polidispesidad baja.
EP2134824A2 (fr) 2007-04-03 2009-12-23 Henkel AG & Co. KGaA Détergents contenant des principes actifs améliorant la détergence primaire
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DE102012223336A1 (de) * 2012-12-17 2014-06-18 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel mit polyalkoxyliertem Polyamin und angepasstem Niotensid

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