EP3218464B1 - Detergents and cleaning agents having improved performance - Google Patents
Detergents and cleaning agents having improved performance Download PDFInfo
- Publication number
- EP3218464B1 EP3218464B1 EP15786973.6A EP15786973A EP3218464B1 EP 3218464 B1 EP3218464 B1 EP 3218464B1 EP 15786973 A EP15786973 A EP 15786973A EP 3218464 B1 EP3218464 B1 EP 3218464B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- stains
- detergents
- compounds
- red
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
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- 125000000913 palmityl 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])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
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- 150000003016 phosphoric acids Chemical class 0.000 description 1
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- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
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- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical class C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- 150000003873 salicylate salts Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 1
- 239000007909 solid dosage form Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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- 239000012209 synthetic fiber Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 108010031354 thermitase Proteins 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- LOIYMIARKYCTBW-OWOJBTEDSA-N trans-urocanic acid Chemical compound OC(=O)\C=C\C1=CNC=N1 LOIYMIARKYCTBW-OWOJBTEDSA-N 0.000 description 1
- LOIYMIARKYCTBW-UHFFFAOYSA-N trans-urocanic acid Natural products OC(=O)C=CC1=CNC=N1 LOIYMIARKYCTBW-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- ORHBXUUXSCNDEV-UHFFFAOYSA-N umbelliferone Chemical compound C1=CC(=O)OC2=CC(O)=CC=C21 ORHBXUUXSCNDEV-UHFFFAOYSA-N 0.000 description 1
- HFTAFOQKODTIJY-UHFFFAOYSA-N umbelliferone Natural products Cc1cc2C=CC(=O)Oc2cc1OCC=CC(C)(C)O HFTAFOQKODTIJY-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3481—Organic compounds containing sulfur containing sulfur in a heterocyclic ring, e.g. sultones or sulfolanes
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D3/34—Organic compounds containing sulfur
- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
-
- 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 certain quinoline derivatives in detergents to improve the washing performance.
- the polymerizable substances are, above all, 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 beverages containing corresponding dyes.
- the stains can be, in particular, stains of fruits or vegetables or even red wine stains, which in particular contain polyphenolic dyes, especially those from the class of anthocyanidins or anthocyanins.
- the European patent application EP 0 132 765 A1 discloses metal detergent containing, in addition to nonionic and / or anionic surfactant and aminocarboxylates, compounds having a five-membered ring having 1 N atom and 1 S atom or 3 S atoms, or a hydroxyquinoline derivative.
- N-atom optionally substituted with organic groups such as the methyl, ethyl, propyl, phenyl, naphthyl or carboxyethyl group, substituted 4-pyridinones for the removal of stains from textiles is known from the international patent application WO 2007/042140 A2 known.
- a first subject of the present invention is therefore the use of compounds of general formula (I), in which R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another are hydrogen or SO 3 X, with the proviso that at least 1 of said radicals R 1 to R 6 is not hydrogen, and X is Is hydrogen, an alkali metal or ammonium,
- the bleachable stains usually contain polymerizable substances, in particular polymerizable dyes, wherein the polymerizable dyes are preferably polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds.
- polymerizable dyes are preferably polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds.
- stains in intermediate colors in particular violet, purple, brown, purple or pink
- stains which are green, yellow, red and violet
- the colors mentioned can also be light or dark in each case.
- stains in particular stains of grass, fruits or vegetables, in particular stains caused by food products, such as Spices, sauces, chutneys, curries, purees and marmalades, or beverages, such as coffee, tea, wines and juices containing corresponding green, yellow, red, purple, purple, brown, purple, pink and / or blue dyes.
- food products such as Spices, sauces, chutneys, curries, purees and marmalades
- beverages such as coffee, tea, wines and juices containing corresponding green, yellow, red, purple, purple, brown, purple, pink and / or blue dyes.
- the stains to be removed according to the invention can be caused in particular by cherry, morelle, grape, apple, pomegranate, aronia, plum, sea buckthorn, acai, kiwi, mango, grass, or berries, especially by red or black currants, elderberries, blackberries, raspberries , Blueberries, cranberries, cranberries, strawberries or blueberries, with coffee, tea, red cabbage, blood orange, eggplant, tomato, carrot, beetroot, spinach, paprika, red meat or potato, or red onion.
- the compounds of general formula (I) are preferably 1 to 4, in particular 1 to 2 SO 3 X - substituents.
- R 4 is an SO 3 X substituent.
- Preferred alkali metals for X are sodium and potassium and mixtures thereof.
- the ammonium ions for X are in addition to NH 4 + and a total of 1 to 4 C 1-12 alkyl groups and / or C 2-5 hydroxyalkyl groups carrying ammonium groups.
- the use according to the invention of the compound of the general formula (I) is preferably carried out in detergents by adding them in an amount of from 0.01% by weight to 10% by weight, in particular in an amount of 0.05% by weight. to 5 wt .-%, is used, wherein here and below, the information of "wt .-%" each relate to the weight of the total detergent.
- Another object of the invention is therefore a liquid laundry detergent containing no oxidative bleach containing builders and a compound of general formula (I) in an amount of preferably 0.01 wt .-% to 10 wt .-%, in particular 0, 05 wt .-% to 5 wt .-%, wherein the above or below described preferred embodiments also apply to this subject of the invention.
- Such an agent is employed in conventional automated or manual washing processes in which soiled laundry is exposed to an aqueous liquor containing the agent with the aim of removing the soiling from the textile surface.
- the detergent does not contain any oxidative bleaches
- the agent contains no oxidative bleaching agents in the narrower sense, to which hypochlorites, hydrogen peroxide or hydrogen peroxide-yielding substances and peroxyacids are to be expected; preferably, it also has no bleach activators and / or bleach catalysts.
- the detergents may contain other usual constituents of textile detergents, in particular those selected from the group of surfactants and preferably polymers, enzymes, disintegration aids, fragrances and perfume carriers.
- the builders include in particular the zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological prejudices against their use - also the phosphates.
- the finely crystalline zeolite containing synthetic and bound water is preferably zeolite A and / or zeolite P.
- Zeolite P is, for example, zeolite MAP® (commercial product from Crosfield).
- zeolite X and mixtures of zeolite A, X and / or P are also suitable, however, are zeolite X and mixtures of zeolite A, X and / or P.
- Commercially available and usable in the context of the present invention is, for example, also a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
- the zeolite can be used both as a builder in a granular compound, as well as for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, usually both ways for incorporating the zeolite are used in the premix.
- Zeolites may have an average particle size of less than 10 ⁇ m (volume distribution, Coulter Counter method) and preferably contain from 18% to 22% by weight, in particular from 20% to 22% by weight, of bound water.
- crystalline layer-form silicates of the general formula NaMSi x O 2x + 1 .yH 2 O in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
- the crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 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 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
- both ⁇ - and ⁇ -sodium are Na 2 Si 2 O 5 .yH 2 O and furthermore especially Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -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 H 2 O, 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 ).
- Washing or cleaning agents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 ⁇ y H 2 O of from 0.1% by weight to 20% by weight, preferably from 0.2% by weight 15 wt .-% and in particular from 0.4 wt .-% to 10 wt .-%.
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 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 preferably Ittleverzögert and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- amorphous is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most cause one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle.
- X-ray-amorphous silicates whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such X-ray amorphous silicates also have a dissolution delay compared to the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
- silicate (s) preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali metal disilicates, if present, are present in detergents or cleaners in amounts of from 3% by weight to 60% by weight, preferably 8% by weight. % to 50 wt .-% and in particular from 20 wt .-% to 40 wt .-%.
- phosphates As builders, if such use is not to be avoided for ecological reasons.
- alkali metal phosphates with particular preference of pentasodium and Pentakaliumtriphosphat (sodium and potassium tripolyphosphate) in the detergent and cleaning industry have the greatest importance.
- Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
- the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to the cleaning performance.
- Technically particularly important phosphates are the 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).
- preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 5% to 80 wt .-%, preferably from 15 wt .-% to 75 wt .-% and in particular from 20 wt .-% to 70 wt .-%.
- alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.
- Particularly preferred may be a builder system containing a mixture of tripolyphosphate and sodium carbonate.
- the alkali metal hydroxides are usually only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 Wt .-% and in particular below 2 wt .-%, used.
- Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
- Particularly suitable organic builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and also phosphonates.
- Useful are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
- NTA nitrilotriacetic acid
- the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
- an acidifying component In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
- Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 g / mol to 70000 g / mol.
- Particularly suitable are polyacrylates which preferably have a molecular weight of from 2000 g / mol to 20 000 g / mol.
- the short-chain polyacrylates which have molecular weights of from 2000 g / mol to 10000 g / mol, and particularly preferably from 3000 g / mol to 5000 g / mol, may again be preferred from this group.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50% by weight to 90% by weight of acrylic acid and 50% by weight to 10% by weight of maleic acid have proven to be particularly suitable.
- the relative molecular weight, based on free acids, is generally from 2000 g / mol to 70000 g / mol, preferably from 20 000 g / mol to 50 000 g / mol and in particular from 30 000 g / mol to 40 000 g / mol.
- the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
- the (co) polymeric polycarboxylates can be used as a solid or in aqueous solution.
- the content of detergents or cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5% by weight to 20% by weight and in particular from 3% by weight to 10% by weight.
- biodegradable polymers of more than two different monomer units for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives.
- Other preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- polyaspartic acids and / or their salts are particularly preferred.
- phosphonates are the salts of, in particular, hydroxyalkane or aminoalkanephosphonic acids.
- hydroxyalkanephosphonic acids 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance. It is used in particular as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline.
- Particularly suitable aminoalkanephosphonic acids are ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs.
- the neutral-reacting sodium salts for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.
- Mixtures of the mentioned phosphonates can also be used as organic builders.
- the aminoalkanephosphonates also have a pronounced heavy metal binding capacity.
- polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C 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.
- Suitable organic builders are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
- it is hydrolysis products having average molecular weights in the range of 400 g / mol to 500000 g / mol.
- a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
- DE dextrose equivalent
- 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.
- Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
- ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
- glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
- suitable amounts are in particular in zeolite-containing and / or silicate-containing formulations at 3 wt .-% to 15 wt .-%.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids and their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
- Detergents and cleaners may contain nonionic, anionic, cationic and / or amphoteric surfactants.
- nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
- Detergents or cleaning agents with particular preference contain nonionic surfactants from the group of alkoxylated alcohols.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
- EO ethylene oxide
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 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 alcohols 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 stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- nonionic surfactants it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- nonionic surfactants and alkyl glycosides of the general Formula RO (G) x are used in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glykoseisme 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 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 having from 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-tallowalkyl-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, especially not more than half thereof.
- polyhydroxy fatty acid amides of the formula wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which 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 R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest.
- [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 catalyst.
- nonionic surfactants from the group of alkoxylated alcohols, more 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 the PO / EO / PO nonionic surfactants are particularly preferred.
- Such PO / EO / PO nonionic surfactants are characterized by good foam control.
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
- alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
- sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 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) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxoate kyote and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of the mentioned Chain length, which contain a synthetic, petrochemical-based straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
- Fettatkohote with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1% by weight to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are 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 derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- anionic surfactants are particularly soaps into consideration.
- Suitable are 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 of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
- the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
- Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer feel and reduced electrostatic charge (increased wearing comfort)
- the active ingredients of these formulations are quaternary ammonium compounds having two hydrophobic radicals, such as the disteraryldimethylammonium chloride, however because of its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
- esters with improved biodegradability are obtainable, 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. Further suitable as a finish is dimethylolethyleneurea.
- Enzymes can be used to increase the performance of detergents or cleaners. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaning agents, which are preferably used accordingly become.
- Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 wt .-% to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
- subtilisin type those of the subtilisin type are preferable.
- these are the 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 no longer be assigned 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 abovementioned amylases, which have been improved for use in detergents and cleaners. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
- lipases or cutinases because of their triglyceride-splitting activity. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed therefrom, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases and / or cutinases whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
- 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 which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
- the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
- the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
- capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
- granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
- enzymes and / or enzyme preparations preferably protease preparations and / or amylase preparations, in amounts of from 0.1% by weight to 5% by weight, preferably from 0.2% by weight to 4 , 5 wt .-% and in particular from 0.4 wt .-% to 4 wt .-%, used.
- perfume oils or fragrances individual perfume compounds, for example synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
- perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- a fragrance In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role.
- fragrances have molecular weights up to about 200 g / mol, while molar masses of 300 g / mol and above are more of an exception.
- the odor of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note, body” as well as " Base note "(end note, dry out). Since odor perception is also largely based on odor intensity, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note is for the most part consists of less volatile, ie adherent fragrances.
- fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
- fixatives for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
- the colorants can have a high storage stability and insensitivity to light as well as not too high an affinity for textile surfaces and, in particular, for synthetic fibers.
- colorants may have different stabilities to oxidation.
- water-insoluble colorants are more stable to oxidation than water-soluble colorants.
- concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 -2 % by weight to 10 -3 % by weight are typically selected.
- the suitable concentration of the colorant in detergents or cleaners is typically from about 10 -3 % by weight to 10 -4 % by weight.
- Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
- the detergents or cleaning agents may contain further ingredients which further improve the performance and / or aesthetic properties of these agents.
- Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.
- electrolytes from the group of inorganic salts a wide number of different salts can be used.
- Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the washing or cleaning agents is preferred.
- pH adjusters In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Applicable here are all known acids or alkalis, unless their use is prohibited for application or environmental reasons or for reasons of consumer protection. Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation.
- Suitable foam inhibitors are soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials.
- Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials.
- preferred agents include 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 usually are clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1000 g / mol and 150000 g / mol and viscosities between 10 mPa.s and 1000000 mPa.s.
- Suitable soil repellents are known from the prior art polymers of phthalic acid and / or terephthalic acid and derivatives thereof, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate or anionic and / or nonionic modified derivatives of these in question. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
- Optical brighteners may in particular be added to the detergents in order to eliminate graying and yellowing of the treated textiles. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence and the yellow color of the gray or yellowed wash pure white results.
- Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.
- fluoronic acids 4,4'-diamino-2,2'-stilbenedisulfonic acids
- 4,4'-distyrylbiphenyls 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimid
- Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
- Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- water-soluble polyamides containing acidic groups are suitable for this purpose.
- soluble starch preparations can be used, for example degraded starch and aldehyde starches. Polyvinylpyrrolidone is also useful.
- graying inhibitors are cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
- cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.
- nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30 wt .-% and of hydroxypropyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether.
- 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 ester.
- Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability.
- Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical coupled polymerizable compounds.
- Antistatic agents may also be included.
- the antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension.
- a further field of application of repellents and impregnating agents is the water-repellent finish of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing).
- the water repellents used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups.
- Suitable water repellents are, for example, paraffins, waxes, metal soaps, etc.
- hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening.
- silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices 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 bacteriostats and bactericides, fungistatics and fungicides and so on. Substances from these groups are, for example, benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercuriacetate, wherein it is also possible to dispense entirely with these compounds.
- the agents may 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 the surface conductivity and thus allow an improved drainage of formed charges.
- External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided 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 antistatics for textiles and as an additive to detergents, wherein additionally a softening effect is achieved.
- silicone derivatives can be used in laundry detergents. These additionally improve the rinsing out of detergents or cleaning agents by their foam-inhibiting properties.
- Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
- Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or Si-OH, Si-H and / or Si-Cl bonds.
- Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols, and the polyalkylene oxide-modified dimethylpolysiloxanes.
- UV absorbers which are applied to the treated textiles and improve the light resistance of the fibers.
- Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, 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.
- Protein hydrolyzates are due to their fiber-care effect other suitable active substances. Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). Protein hydrolysates of both vegetable and animal origin can be used. Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Preference is given to the use of protein hydrolysates of plant origin, for example soybean, almond, rice, pea, potato and wheat protein hydrolysates.
- protein hydrolyzates are preferred as such, other amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.
- the brightness differences when using the substance essential to the invention were significantly greater than those resulting from the use of the substance-free comparative detergent, which corresponds to a higher whiteness and thus improved stain removal.
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Description
Die vorliegende Erfindung betrifft die Verwendung bestimmter Chinolinderivate in Waschmitteln zur Verbesserung der Waschleistung.The present invention relates to the use of certain quinoline derivatives in detergents to improve the washing performance.
Während die Formulierung pulverförmiger, Bleichmittel enthaltender Wasch- und Reinigungsmittel heute keinerlei Probleme mehr bereitet, stellt die Formulierung stabiler flüssiger, Bleichmittel enthaltender Wasch- und Reinigungsmittel nach wie vor ein Problem dar. Aufgrund des üblicherweise Fehlens des Bleichmittels in flüssigen Wasch- und Reinigungsmitteln werden solche Anschmutzungen, die normalerweise insbesondere aufgrund der enthaltenen Bleichmittel entfernt werden, entsprechend häufig nur in unzureichender Weise entfernt. Ein ähnliches Problem besteht auch für Bleichmittel-freie Color-Waschmittel, bei denen das Bleichmittel weggelassen wird, um die Farbstoffe im Textil zu schonen und deren Ausbleichen zu verhindern. Bei fehlendem Bleichmittel kommt erschwerend hinzu, dass anstatt der Entfernung der sogenannten bleichbaren Anschmutzungen, die normalerweise durch das Bleichmittel auf Persauerstoffbasis wenigstens anteilsweise entfernt werden, aufgrund des Waschvorgangs häufig im Gegenteil sogar eine Intensivierung und/oder Verschlechterung der Entfernbarkeit der Anschmutzung herbeigeführt wird, was nicht zuletzt auf initiierte chemische Reaktionen zurückzuführen sein dürfte, die beispielsweise in der Polymerisierung bestimmter in den Anschmutzungen enthaltener Farbstoffe bestehen können.While the formulation of powdered, bleach-containing detergents and cleaners today no longer causes any problems, the formulation of stable liquid, bleach-containing detergents and cleaners is still a problem dar. Due to the usual lack of bleaching agents in liquid detergents and cleaning agents such Stains, which are usually removed in particular due to the bleach contained, often removed only inadequate. A similar problem also exists for bleach-free color detergents in which the bleaching agent is omitted in order to protect the dyes in the textile and to prevent their bleaching. In the absence of bleaching agents, it is aggravating that instead of removing the so-called bleachable soils which are normally at least partially removed by the peroxygen-based bleaching agent, on the contrary, intensification and / or worsening of the removability of the soiling is often brought about by the washing process may be due to initiated chemical reactions, which may for example in the polymerization of certain dyes contained in the stains.
Derartige Probleme treten insbesondere bei Anschmutzungen auf, die polymerisierbare Substanzen enthalten. Bei den polymerisierbaren Substanzen handelt es sich vor allem um polyphenolische Farbstoffe, vorzugsweise um Flavonoide, insbesondere aus der Klasse der Anthocyanidine oder Anthocyane. Die Anschmutzungen können insbesondere durch Lebensmittelprodukte oder Getränke verursacht worden sein, die entsprechende Farbstoffe enthalten. Bei den Anschmutzungen kann es sich insbesondere um Flecken von Früchten oder Gemüse oder auch Rotweinflecken handeln, die insbesondere polyphenolische Farbstoffe, vor allem solche aus der Klasse der Anthocyanidine oder Anthocyane, enthalten.Such problems occur especially with stains containing polymerizable substances. The polymerizable substances are, above all, 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 beverages containing corresponding dyes. The stains can be, in particular, stains of fruits or vegetables or even red wine stains, which in particular contain polyphenolic dyes, especially those from the class of anthocyanidins or anthocyanins.
Aus der internationalen Patentanmeldung
Die europäische Patentanmeldung
Die americanische Patentanmeldung
Die Verwendung von am N-Atom gegebenenfalls mit organischen Gruppen, wie der Methyl-, Ethyl-, Propyl-, Phenyl-, Napthyl- oder Carboxyethylgruppe, substituierten 4-Pyridinonen zur Entfernung von Anschmutzungen von Textilien ist aus der internationalen Patentanmeldung
Überraschenderweise wurde nun gefunden, dass durch den Einsatz von 8-Hydroxychinolinsulfonsäuren die Wasch oder Reinigungsleistung des Wasch- oder Reinigungsmittels insbesondere in Bezug auf bleichbare Anschmutzungen deutlich verbessert werden kann.Surprisingly, it has now been found that the use of 8-hydroxyquinoline sulfonic acids can markedly improve the washing or cleaning performance of the washing or cleaning agent, in particular with regard to bleachable soiling.
Ein erster Gegenstand der vorliegenden Erfindung ist daher die Verwendung von Verbindungen der allgemeinen Formel (I),
in flüssigen Textilwaschmitteln, die Gerüststoffe und keine oxidativen Bleichmittel enthalten, zur Verbesserung der Wasch- oder Reinigungsleistung gegenüber bleichbaren Anschmutzungen.in liquid laundry detergents containing builders and no oxidative bleaches for improving the washing or cleaning performance of bleachable soils.
Die bleichbaren Anschmutzungen enthalten üblicherweise polymerisierbare Substanzen, insbesondere polymerisierbare Farbstoffe, wobei es sich bei den polymerisierbaren Farbstoffen vorzugsweise um polyphenolische Farbstoffe, insbesondere um Flavonoide, vor allem um Anthocyanidine oder Anthocyane oder Oligomere dieser Verbindungen handelt. Neben der Entfernung von Anschmutzungen in den Farben grün, gelb, rot oder blau kommt auch die von Anschmutzungen in Zwischenfarben, insbesondere violett, lila, braun, purpurfarben oder rosa, und auch von Anschmutzungen in Betracht, die eine grüne, gelbe, rote, violette, lilafarbene, braune, purpurfarbene, rosafarbene oder blaue Tönung aufweisen, ohne im Wesentlichen selbst komplett aus dieser Farbe zu bestehen. Die genannten Farben können insbesondere auch jeweils hell oder dunkel sein. Es handelt sich hierbei vorzugsweise um Anschmutzungen, insbesondere um Flecken von Gras, Früchten oder Gemüse, insbesondere auch um Anschmutzungen durch Lebensmittelprodukte, wie beispielsweise Gewürze, Saucen, Chutneys, Currys, Pürees und Marmeladen, oder Getränke, wie beispielsweise Kaffee, Tee, Weine und Säfte, die entsprechende grüne, gelbe, rote, violette, lilafarbene, braune, purpurfarbene, rosafarbene und/oder blaue Farbstoffe enthalten.The bleachable stains usually contain polymerizable substances, in particular polymerizable dyes, wherein the polymerizable dyes are preferably polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds. In addition to removing stains in the colors green, yellow, red or blue, stains in intermediate colors, in particular violet, purple, brown, purple or pink, as well as stains, which are green, yellow, red and violet, come into consideration Purple, brown, purple, pink or blue tint, without essentially being made entirely of this color itself. The colors mentioned can also be light or dark in each case. These are preferably stains, in particular stains of grass, fruits or vegetables, in particular stains caused by food products, such as Spices, sauces, chutneys, curries, purees and marmalades, or beverages, such as coffee, tea, wines and juices containing corresponding green, yellow, red, purple, purple, brown, purple, pink and / or blue dyes.
Die erfindungsgemäß zu entfernenden Anschmutzungen können insbesondere verursacht sein durch Kirsche, Morelle, Traube, Apfel, Granatapfel, Aronia, Pflaume, Sanddorn, Açai, Kiwi, Mango, Gras, oder Beeren, vor allem durch rote oder schwarze Johannisbeeren, Holunderbeeren, Brombeeren, Himbeeren, Blaubeeren, Preiselbeeren, Kronsbeeren, Erdbeeren oder Heidelbeeren, durch Kaffee, Tee, Rotkohl, Blutorange, Aubergine, Tomate, Karotte, Rote Beete, Spinat, Paprika, rotfleischige oder blaufleischige Kartoffel, oder rote Zwiebel.The stains to be removed according to the invention can be caused in particular by cherry, morelle, grape, apple, pomegranate, aronia, plum, sea buckthorn, acai, kiwi, mango, grass, or berries, especially by red or black currants, elderberries, blackberries, raspberries , Blueberries, cranberries, cranberries, strawberries or blueberries, with coffee, tea, red cabbage, blood orange, eggplant, tomato, carrot, beetroot, spinach, paprika, red meat or potato, or red onion.
In den Verbindungen der allgemeinen Formel (I) sind vorzugsweise 1 bis 4, insbesondere 1 bis 2 SO3X - Substituenten enthalten. Vorzugsweise ist R4 ein SO3X - Substituent. Bevorzugte Alkalimetalle für X sind Natrium und Kalium und deren Gemische. Unter den Ammoniumionen für X sind neben NH4 + auch insgesamt 1 bis 4 C1-12 -Alkylgruppen und/oder C2-5-Hydroxyalkylgruppen tragende Ammoniumgruppen.In the compounds of general formula (I) are preferably 1 to 4, in particular 1 to 2 SO 3 X - substituents. Preferably, R 4 is an SO 3 X substituent. Preferred alkali metals for X are sodium and potassium and mixtures thereof. Among the ammonium ions for X are in addition to NH 4 + and a total of 1 to 4 C 1-12 alkyl groups and / or C 2-5 hydroxyalkyl groups carrying ammonium groups.
Die erfindungsgemäße Verwendung der Verbindung der allgemeinen Formel (I) erfolgt in Waschmitteln vorzugsweise dadurch, dass man sie in einer Menge von 0,01 Gew.-% bis 10 Gew.-%, insbesondere in einer Menge von 0,05 Gew.-% bis 5 Gew.-%, einsetzt, wobei sich hier und im Folgenden die Angaben von "Gew.-%" jeweils auf das Gewicht des gesamten Waschmittels beziehen. Ein weiterer Gegenstand der Erfindung ist daher ein flüssiges Textilwaschmittel, das keine oxidativen Bleichmittel enthält, enthaltend Gerüststoffe und eine Verbindung der allgemeinen Formel (I) in einer Menge von vorzugsweise 0,01 Gew.-% bis 10 Gew.-%, insbesondere 0,05 Gew.-% bis 5 Gew.-%, wobei die vor- oder nachstehend beschriebenen bevorzugten Ausführungsformen auch für diesen Gegenstand der Erfindung gelten. Ein solches Mittel wird in üblichen maschinell oder manuell auszuführenden Waschverfahren eingesetzt, bei denen verschmutze Wäsche einer das Mittel enthaltenden wässrigen Flotte ausgesetzt wird mit dem Ziel, die Anschmutzung von der textilen Oberfläche zu entfernen.The use according to the invention of the compound of the general formula (I) is preferably carried out in detergents by adding them in an amount of from 0.01% by weight to 10% by weight, in particular in an amount of 0.05% by weight. to 5 wt .-%, is used, wherein here and below, the information of "wt .-%" each relate to the weight of the total detergent. Another object of the invention is therefore a liquid laundry detergent containing no oxidative bleach containing builders and a compound of general formula (I) in an amount of preferably 0.01 wt .-% to 10 wt .-%, in particular 0, 05 wt .-% to 5 wt .-%, wherein the above or below described preferred embodiments also apply to this subject of the invention. Such an agent is employed in conventional automated or manual washing processes in which soiled laundry is exposed to an aqueous liquor containing the agent with the aim of removing the soiling from the textile surface.
Unter dem Merkmal, dass das Waschmittel keine oxidativen Bleichmittel enthält, ist zu verstehen, dass das Mittel keine oxidativen Bleichmittel im engeren Sinne, zu denen Hypochlorite, Wasserstoffperoxid oder Wasserstoffperoxid liefernde Substanzen und Peroxosäuren zu rechnen sind, enthält; vorzugsweise weist es auch keine Bleichaktivatoren und/oder Bleichkatalysatoren auf.By the feature that the detergent does not contain any oxidative bleaches is to be understood that the agent contains no oxidative bleaching agents in the narrower sense, to which hypochlorites, hydrogen peroxide or hydrogen peroxide-yielding substances and peroxyacids are to be expected; preferably, it also has no bleach activators and / or bleach catalysts.
Die Waschmittel können neben dem erfindungswesentlichen Wirkstoff übliche sonstige Bestandteile von Textilwaschmitteln enthalten, insbesondere ausgewählt aus der Gruppe der Tenside sowie vorzugsweise der Polymere, Enzyme, Desintegrationshilfsmittel, Duftstoffe und Parfümträger.In addition to the active substance essential to the invention, the detergents may contain other usual constituents of textile detergents, in particular those selected from the group of surfactants and preferably polymers, enzymes, disintegration aids, fragrances and perfume carriers.
Zu den Gerüststoffe zählen insbesondere die Zeolithe, Silikate, Carbonate, organische Cobuilder und - sofern keine ökologischen Vorurteile gegen ihren Einsatz bestehen - auch die Phosphate.The builders include in particular the zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological prejudices against their use - also the phosphates.
Der feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise Zeolith A und/oder Zeolith P. Als Zeolith P kommt beispielsweise Zeolith MAP® (Handelsprodukt der Firma Crosfield) in Frage. Geeignet sind jedoch auch Zeolith X sowie Mischungen aus Zeolith A, X und/oder P. Kommerziell erhältlich und im Rahmen der vorliegenden Erfindung einsetzbar ist beispielsweise auch ein Co-Kristallisat aus Zeolith X und Zeolith A (ca. 80 Gew.-% Zeolith X), das durch die Formel
nNa2O · (1-n)K2O · Al2O3 · (2 - 2,5)SiO2 · (3,5 - 5,5)H2O
beschrieben werden kann. Der Zeolith kann dabei sowohl als Gerüststoff in einem granularen Compound eingesetzt, als auch zu einer Art "Abpuderung" einer granularen Mischung, vorzugsweise einer zu verpressenden Mischung verwendet werden, wobei üblicherweise beide Wege zur Inkorporation des Zeoliths in das Vorgemisch genutzt werden. Zeolithe können eine mittlere Teilchengröße von weniger als 10 µm (Volumenverteilung; Meßmethode: Coulter Counter) aufweisen und enthalten vorzugsweise 18 Gew.-% bis 22 Gew.-%, insbesondere 20 Gew.-% bis 22 Gew.-% an gebundenem Wasser.The finely crystalline zeolite containing synthetic and bound water is preferably zeolite A and / or zeolite P. Zeolite P is, for example, zeolite MAP® (commercial product from Crosfield). Also suitable, however, are zeolite X and mixtures of zeolite A, X and / or P. Commercially available and usable in the context of the present invention is, for example, also a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), by the formula
nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O
can be described. The zeolite can be used both as a builder in a granular compound, as well as for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, usually both ways for incorporating the zeolite are used in the premix. Zeolites may have an average particle size of less than 10 μm (volume distribution, Coulter Counter method) and preferably contain from 18% to 22% by weight, in particular from 20% to 22% by weight, of bound water.
Es können auch kristalline schichtförmige Silikate der allgemeinen Formel NaMSixO2x+1 · y H2O eingesetzt werden, worin M Natrium oder Wasserstoff darstellt, x eine Zahl von 1,9 bis 22, vorzugsweise von 1,9 bis 4 ist, wobei besonders bevorzugte Werte für x 2, 3 oder 4 sind, und y für eine Zahl von 0 bis 33, vorzugsweise von 0 bis 20 steht. Die kristallinen schichtförmigen Silikate der Formel NaMSixO2x+1 · y H2O werden beispielsweise von der Firma Clariant GmbH (Deutschland) unter dem Handelsnamen Na-SKS vertrieben. Beispiele für diese Silikate sind Na-SKS-1 (Na2Si22O45 · x H2O, Kenyait), Na-SKS-2 (Na2Si14O29 · x H2O, Magadiit), Na-SKS-3 (Na2Si8O17 · x H2O) oder Na-SKS-4 (Na2Si4O9 · x H2O, Makatit).It is also possible to use crystalline layer-form silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layer-form silicates of the formula NaMSi x O 2x + 1 .yH 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 .xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
Bevorzugt sind kristalline Schichtsilikate der Formel NaMSixO2x+1 · y H2O, in denen x für 2 steht. Insbesondere sind sowohl ß- als auch δ-Natriumdisitikate Na2Si2O5 · y H2O sowie weiterhin vor allem Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (ß-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O5 · H2O), Na-SKS-10 (NaHSi2O5 · 3 H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS-13 (NaHSi2O5), insbesondere aber Na-SKS-6 (δ-Na2Si2O5) bevorzugt. Wasch- oder Reinigungsmittel enthalten vorzugsweise einen Gewichtsanteil des kristallinen schichtförmigen Silikats der Formel NaMSixO2x+1 · y H2O von 0,1 Gew.-% bis 20 Gew.-%, bevorzugt von 0,2 Gew.-% bis 15 Gew.-% und insbesondere von 0,4 Gew.-% bis 10 Gew.-%.Preference is given to crystalline phyllosilicates of the formula NaMSi x O 2x + 1 .yH 2 O, in which x is 2. In particular, both β- and δ-sodium are Na 2 Si 2 O 5 .yH 2 O and furthermore especially Na-SKS-5 (α-Na 2 Si 2 O 5 ), Na-SKS-7 (β-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 H 2 O, kanemite), Na-SKS-11 ( t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 (δ-Na 2 Si 2 O 5 ). Washing or cleaning agents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 · y H 2 O of from 0.1% by weight to 20% by weight, preferably from 0.2% by weight 15 wt .-% and in particular from 0.4 wt .-% to 10 wt .-%.
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche vorzugsweise Iöseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Unter dem Begriff "amorph" wird verstanden, dass die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen, hervorrufen.It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 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 preferably Iöseverzögert and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. The term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most cause one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle.
Alternativ oder in Kombination mit den vorgenannten amorphen Natriumsilikaten können röntgenamorphe Silikate eingesetzt werden, deren Silikatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, dass die Produkte mikrokristalline Bereiche der Größe zehn bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Derartige röntgenamorphe Silikate weisen ebenfalls eine Löseverzögerung gegenüber den herkömmlichen Wassergläsern auf. Insbesondere bevorzugt sind verdichtete/kompaktierte amorphe Silikate, compoundierte amorphe Silikate und übertrocknete röntgenamorphe Silikate.Alternatively or in combination with the abovementioned amorphous sodium silicates, it is possible to use X-ray-amorphous silicates whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
Diese(s) Silikat(e), vorzugsweise Alkalisilikate, besonders bevorzugt kristalline oder amorphe Alkalidisilikate, sind, wenn vorhanden, in Wasch- oder Reinigungsmitteln in Mengen von 3 Gew.-% bis 60 Gew.-%, vorzugsweise von 8 Gew.-% bis 50 Gew.-% und insbesondere von 20 Gew.-% bis 40 Gew.-% enthalten.These silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali metal disilicates, if present, are present in detergents or cleaners in amounts of from 3% by weight to 60% by weight, preferably 8% by weight. % to 50 wt .-% and in particular from 20 wt .-% to 40 wt .-%.
Auch ein Einsatz der allgemein bekannten Phosphate als Buildersubstanzen ist möglich, sofern ein derartiger Einsatz nicht aus ökologischen Gründen vermieden werden soll. Unter der Vielzahl der kommerziell erhältlichen Phosphate haben die Alkalimetallphosphate unter besonderer Bevorzugung von Pentanatrium- und Pentakaliumtriphosphat (Natrium- und Kaliumtripolyphosphat) in der Wasch- und Reinigungsmittel-Industrie die größte Bedeutung.It is also possible to use the generally known phosphates as builders, if such use is not to be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference of pentasodium and Pentakaliumtriphosphat (sodium and potassium tripolyphosphate) in the detergent and cleaning industry have the greatest importance.
Alkalimetallphosphate ist dabei die summarische Bezeichnung für die Alkalimetall- (insbesondere Natrium- und Kalium-) Salze der verschiedenen Phosphorsäuren, bei denen man Metaphosphorsäuren (HPO3)n und Orthophosphorsäure H3PO4 neben höhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken als Alkaliträger, verhindern Kalkbeläge auf Maschinenteilen und Kalkinkrustationen in Geweben und tragen überdies zur Reinigungsleistung bei. Technisch besonders wichtige Phosphate sind das Pentanatriumtriphosphat, Na5P3O10 (Natriumtripolyphosphat) sowie das entsprechende Kaliumsalz Pentakaliumtriphosphat, K5P3O10 (Kaliumtripolyphosphat). Bevorzugt eingesetzt werden weiterhin die Natriumkaliumtripolyphosphate. Werden Phosphate in Wasch- oder Reinigungsmitteln eingesetzt, so enthalten bevorzugte Mittel diese(s) Phosphat(e), vorzugsweise Alkalimetallphosphat(e), besonders bevorzugt Pentanatrium- oder Pentakaliumtriphosphat (Natrium- oder Kaliumtripolyphosphat), in Mengen von 5 Gew.-% bis 80 Gew.-%, vorzugsweise von 15 Gew.-% bis 75 Gew.-% und insbesondere von 20 Gew.-% bis 70 Gew.-%.Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to the cleaning performance. Technically particularly important phosphates are the 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). Preference is furthermore given to using the sodium potassium tripolyphosphates. If phosphates are used in detergents or cleaners, preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of from 5% to 80 wt .-%, preferably from 15 wt .-% to 75 wt .-% and in particular from 20 wt .-% to 70 wt .-%.
Weiter einsetzbar sind Alkaliträger. Als Alkaliträger gelten beispielsweise Alkalimetallhydroxide, Alkalimetallcarbonate, Alkalimetallhydrogencarbonate, Alkalimetallsesquicarbonate, die genannten Alkalisilikate, Alkalimetasilikate, und Mischungen der vorgenannten Stoffe, wobei bevorzugt die Alkalicarbonate, insbesondere Natriumcarbonat, Natriumhydrogencarbonat oder Natriumsesquicarbonat eingesetzt werden. Besonders bevorzugt kann ein Buildersystem enthaltend eine Mischung aus Tripolyphosphat und Natriumcarbonat sein. Aufgrund ihrer im Vergleich mit anderen Buildersubstanzen geringen chemischen Kompatibilität mit den übrigen Inhaltsstoffen von Wasch- oder Reinigungsmitteln werden die Alkalimetallhydroxide üblicherweise nur in geringen Mengen, vorzugsweise in Mengen unterhalb 10 Gew.-%, bevorzugt unterhalb 6 Gew.-%, besonders bevorzugt unterhalb 4 Gew.-% und insbesondere unterhalb 2 Gew.-%, eingesetzt. Besonders bevorzugt werden Mittel, welche bezogen auf ihr Gesamtgewicht weniger als 0,5 Gew.-% und insbesondere keine Alkalimetallhydroxide enthalten. Bevorzugt ist der Einsatz von Carbonat(en) und/oder Hydrogencarbonat(en), vorzugsweise Alkalicarbonat(en), besonders bevorzugt Natriumcarbonat, in Mengen von 2 Gew.-% bis 50 Gew.-%, vorzugsweise von 5 Gew.-% bis 40 Gew.-% und insbesondere von 7,5 Gew.-% bis 30 Gew.-%.Further usable are alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. Particularly preferred may be a builder system containing a mixture of tripolyphosphate and sodium carbonate. Because of their low chemical compatibility with the other ingredients of detergents or cleaning agents compared with other builders, the alkali metal hydroxides are usually only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 Wt .-% and in particular below 2 wt .-%, used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides. Preference is given to the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2% to 50%, preferably from 5% to 40% and more preferably from 7.5% to 30% by weight wt .-%.
Als organische Builder sind insbesondere Polycarboxylate/Polycarbonsäuren, polymere Polycarboxylate, Asparaginsäure, Polyacetale, Dextrine sowie Phosphonate zu nennen. Brauchbar sind beispielsweise die in Form der freien Säure und/oder ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Die freien Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- oder Reinigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen. Als Gerüststoffe sind weiter polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 g/mol bis 70000 g/mol. Geeignet sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 2000 g/mol bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 2000 g/mol bis 10000 g/mol, und besonders bevorzugt von 3000 g/mol bis 5000 g/mol, aufweisen, bevorzugt sein. Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 Gew.-% bis 90 Gew.-% Acrylsäure und 50 Gew.-% bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2000 g/mol bis 70000 g/mol, vorzugsweise 20000 g/mol bis 50000 g/mol und insbesondere 30000 g/mol bis 40000 g/mol. Zur Verbesserung der Wasserlöslichkeit können die Polymere auch Allylsulfonsäuren, wie beispielsweise Allyloxybenzolsulfonsäure und Methallylsulfonsäure, als Monomer enthalten. Die (co-)polymeren Polycarboxylate können als Feststoff oder in wässriger Lösung eingesetzt werden. Der Gehalt von Wasch- oder Reinigungsmitteln an (co-)polymeren Polycarboxylaten beträgt vorzugsweise 0,5 Gew.-% bis 20 Gew.-% und insbesondere 3 Gew.-% bis 10 Gew.-%.Particularly suitable organic builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and also phosphonates. Useful are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 g / mol to 70000 g / mol. Particularly suitable are polyacrylates which preferably have a molecular weight of from 2000 g / mol to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2000 g / mol to 10000 g / mol, and particularly preferably from 3000 g / mol to 5000 g / mol, may again be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50% by weight to 90% by weight of acrylic acid and 50% by weight to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 g / mol to 70000 g / mol, preferably from 20 000 g / mol to 50 000 g / mol and in particular from 30 000 g / mol to 40 000 g / mol. To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer. The (co) polymeric polycarboxylates can be used as a solid or in aqueous solution. The content of detergents or cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5% by weight to 20% by weight and in particular from 3% by weight to 10% by weight.
Insbesondere bevorzugt sind auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol oder Vinylalkohol-Derivate oder die als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten. Weitere bevorzugte Copolymere sind solche, die als Monomere Acrolein und Acrylsäure/Acrylsäuresalze oder Acrolein und Vinylacetat aufweisen. Ebenso sind als weitere bevorzugte Buildersubstanzen polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren und/oder deren Salze.Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives. Other preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids and / or their salts.
Eine weitere Substanzklasse mit Buildereigenschaften stellen die Phosphonate dar. Dabei handelt es sich um die Salze von insbesondere Hydroxyalkan- oder Aminoalkanphosphonsäuren. Unter den Hydroxyalkanphosphonsäuren ist die 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) von besonderer Bedeutung. Sie wird insbesondere als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch reagiert. Als Aminoalkanphosphonsäuren kommen insbesondere Ethylendiamintetramethylenphosphonsäure (EDTMP), Diethylentriaminpentamethylenphosphonsäure (DTPMP) sowie deren höhere Homologe in Frage. Sie werden insbesondere in Form der neutral reagierenden Natriumsalze, so zum Beispiel als Hexanatriumsalz der EDTMP oder als Hepta- und Octa-Natriumsalz der DTPMP, eingesetzt. Auch Mischungen aus den genannten Phosphonaten können als organische Builder verwendet werden. Insbesondere die Aminoalkanphosphonate besitzen zudem ein ausgeprägtes Schwermetallbindevermögen.Another class of substances with builder properties are the phosphonates. These are the salts of, in particular, hydroxyalkane or aminoalkanephosphonic acids. Among the hydroxyalkanephosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance. It is used in particular as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline. Particularly suitable aminoalkanephosphonic acids are ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs. They are used in particular in the form of the neutral-reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. Mixtures of the mentioned phosphonates can also be used as organic builders. In particular, the aminoalkanephosphonates also have a pronounced heavy metal binding capacity.
Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C 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.
Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere oder Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 g/mol bis 500000 g/mol. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30 bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbar sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch sogenannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2000 g/mol bis 30000 g/mol. Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, welche in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren.Other suitable organic builders are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 g / mol to 500000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 g / mol to 30,000 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.
Auch Oxydisuccinate und andere Derivate von Disuccinaten, vorzugsweise Ethylendiamindisuccinat, sind weitere geeignete Cobuilder. Dabei wird Ethylendiamin-N,N'-disuccinat (EDDS) bevorzugt in Form seiner Natrium- oder Magnesiumsalze verwendet. Weiterhin bevorzugt sind in diesem Zusammenhang auch Glycerindisuccinate und Glycerintrisuccinate. Gewünschtenfalls geeignete Einsatzmengen liegen insbesondere in zeolithhaltigen und/oder silicathaltigen Formulierungen bei 3 Gew.-% bis 15 Gew.-%.Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. If desired, suitable amounts are in particular in zeolite-containing and / or silicate-containing formulations at 3 wt .-% to 15 wt .-%.
Weitere brauchbare organische Cobuilder sind beispielsweise acetylierte Hydroxycarbonsäuren und deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4 Kohlenstoffatome und mindestens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten.Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids and their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
Darüber hinaus können alle Verbindungen, die in der Lage sind, Komplexe mit Erdalkaliionen auszubilden, als Gerüststoffe eingesetzt werden.In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.
Wasch- und Reinigungsmittel können nichtionische, anionische, kationische und/oder amphotere Tenside enthalten.Detergents and cleaners may contain nonionic, anionic, cationic and / or amphoteric surfactants.
Als nichtionische Tenside können alle dem Fachmann bekannten nichtionischen Tenside eingesetzt werden. Mit besonderem Vorzug enthalten Wasch- oder Reinigungsmittel nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole. Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann oder lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 Mol EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO oder 4 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 5 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt einer ganzen oder einer gebrochenen Zahl entsprechen können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE).As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Detergents or cleaning agents with particular preference contain nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 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 alcohols 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 stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
Alternativ oder zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO. Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einem primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen entspricht und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.Alternatively or in addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In addition, as further nonionic surfactants and alkyl glycosides of the general Formula RO (G) x are used in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glykoseeinheit 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.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette.Another class of preferred nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können eingesetzt werden. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-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, especially not more than half thereof.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel
In Reinigungsmitteln sind Niotenside aus der Gruppe der alkoxylierten Alkohole, besonders bevorzugt aus der Gruppe der gemischt alkoxylierten Alkohole und insbesondere aus der Gruppe der EO/AO/EO-Niotenside, oder der PO/AO/PO-Niotenside, speziell der PO/EO/PO-Niotenside besonders bevorzugt. Solche PO/EO/PO-Niotenside zeichnen sich durch gute Schaumkontrolle aus.In cleaning agents are nonionic surfactants from the group of alkoxylated alcohols, more 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 the PO / EO / PO nonionic surfactants are particularly preferred. Such PO / EO / PO nonionic surfactants are characterized by good foam control.
Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse oder Neutralisation gewonnen werden. Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren geeignet.As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure.Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettatkohote, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoatkohote und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt.Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxoate kyote and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of the mentioned Chain length, which contain a synthetic, petrochemical-based straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettatkohote mit 1 bis 4 EO, sind geeignet. Sie werden in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 Gew.-% bis 5 Gew.-%, eingesetzt.The sulfuric acid monoesters of straight-chain or branched C 7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12-18 . Fettatkohote with 1 to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1% by weight to 5% by weight.
Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen, darstellen. Bevorzugte Sulfosuccinate enthalten C8-18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with 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 derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische.As further anionic surfactants are particularly soaps into consideration. Suitable are 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 of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
An Stelle der genannten Tenside oder in Verbindung mit ihnen können auch kationische und/oder amphotere Tenside eingesetzt werden.Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.
Als kationische Aktivsubstanzen können beispielsweise kationische Verbindungen der nachfolgenden Formeln eingesetzt werden:
Zur Pflege der Textilien und zur Verbesserung der Textileigenschaften wie einem weicheren "Griff (Avivage) und verringerter elektrostatischer Aufladung (erhöhter Tragekomfort) können textilweichmachende Verbindungen eingesetzt werden. Die Wirkstoffe dieser Formulierungen sind quartäre Ammoniumverbindungen mit zwei hydrophoben Resten, wie beispielsweise das Disteraryldimethylammoniumchlorid, welches jedoch wegen seiner ungenügenden biologischen Abbaubarkeit zunehmend durch quartäre Ammoniumverbindungen ersetzt wird, die in ihren hydrophoben Resten Estergruppen als Sollbruchstellen für den biologischen Abbau enthalten.Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer feel and reduced electrostatic charge (increased wearing comfort) The active ingredients of these formulations are quaternary ammonium compounds having two hydrophobic radicals, such as the disteraryldimethylammonium chloride, however because of its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
Derartige "Esterquats" mit verbesserter biologischer Abbaubarkeit sind beispielsweise dadurch erhältlich, dass man Mischungen von Methyldiethanolamin und/oder Triethanolamin mit Fettsäuren verestert und die Reaktionsprodukte anschließend in an sich bekannter Weise mit Alkylierungsmitteln quaterniert. Als Appretur weiterhin geeignet ist Dimethylolethylenharnstoff.Such "esterquats" with improved biodegradability are obtainable, 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. Further suitable as a finish is dimethylolethyleneurea.
Zur Steigerung der Leistung von Wasch- oder Reinigungsmitteln sind Enzyme einsetzbar. Hierzu gehören insbesondere Proteasen, Amylasen, Lipasen, Hemicellulasen, Cellulasen, Perhydrolasen oder Oxidoreduktasen, sowie vorzugsweise deren Gemische. Diese Enzyme sind im Prinzip natürlichen Ursprungs; ausgehend von den natürlichen Molekülen stehen für den Einsatz in Wasch- und Reinigungsmitteln verbesserte Varianten zur Verfügung, die entsprechend bevorzugt eingesetzt werden. Wasch- oder Reinigungsmittel enthalten Enzyme vorzugsweise in Gesamtmengen von 1 x 10-6 Gew.-% bis 5 Gew.-% bezogen auf aktives Protein. Die Proteinkonzentration kann mit Hilfe bekannter Methoden, zum Beispiel dem BCA-Verfahren oder dem Biuret-Verfahren bestimmt werden.Enzymes can be used to increase the performance of detergents or cleaners. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaning agents, which are preferably used accordingly become. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 -6 wt .-% to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
Unter den Proteasen sind solche vom Subtilisin-Typ bevorzugt. Beispiele hierfür sind die Subtilisine BPN' und Carlsberg sowie deren weiterentwickelte Formen, die Protease PB92, die Subtilisine 147 und 309, die Alkalische Protease aus Bacillus lentus, Subtilisin DY und die den Subtilasen, nicht mehr jedoch den Subtilisinen im engeren Sinne zuzuordnenden Enzyme Thermitase, Proteinase K und die Proteasen TW3 und TW7.Among the proteases, those of the subtilisin type are preferable. Examples of these are the 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 no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
Beispiele für einsetzbare Amylasen sind die α-Amylasen aus Bacillus licheniformis, aus B. amyloliquefaciens, aus B. stearothermophilus, aus Aspergillus niger und A. oryzae sowie die für den Einsatz in Wasch- und Reinigungsmitteln verbesserten Weiterentwicklungen der vorgenannten Amylasen. Des Weiteren sind für diesen Zweck die α-Amylase aus Bacillus sp. A 7-7 (DSM 12368) und die Cyclodextrin-Glucanotransferase (CGTase) aus B. agaradherens (DSM 9948) hervorzuheben.Examples of usable amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, as well as the further developments of the abovementioned amylases, which have been improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
Einsetzbar sind wegen ihrer Triglycerid-spaltenden Aktivität Lipasen oder Cutinasen. Hierzu gehören beispielsweise die ursprünglich aus Humicola lanuginosa (Thermomyces lanuginosus) erhältlichen oder aus diesen weiterentwickelten Lipasen, insbesondere solche mit dem Aminosäureaustausch D96L. Des Weiteren sind beispielsweise die Cutinasen einsetzbar, die ursprünglich aus Fusarium solani pisi und Humicola insolens isoliert worden sind. Einsetzbar sind weiterhin Lipasen und/oder Cutinasen, deren Ausgangsenzyme ursprünglich aus Pseudomonas mendocina und Fusarium solanii isoliert worden sind.It is possible to use lipases or cutinases because of their triglyceride-splitting activity. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed therefrom, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases and / or cutinases whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
Weiterhin können Enzyme eingesetzt werden, die unter dem Begriff Hemicellulasen zusammengefasst werden. Hierzu gehören beispielsweise Mannanasen, Xanthanlyasen, Pektinlyasen (=Pektinasen), Pektinesterasen, Pektatlyasen, Xyloglucanasen (=Xylanasen), Pullulanasen und β-Glucanasen.Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.
Zur Erhöhung der bleichenden Wirkung können gewünschtenfalls Oxidoreduktasen, beispielsweise Oxidasen, Oxygenasen, Katalasen, Peroxidasen, wie Halo-, Chloro-, Bromo-, Lignin-, Glucose- oder Mangan-peroxidasen, Dioxygenasen oder Laccasen (Phenoloxidasen, Polyphenoloxidasen) eingesetzt werden. Vorteilhafterweise werden zusätzlich vorzugsweise organische, besonders bevorzugt aromatische, mit den Enzymen wechselwirkende Verbindungen zugegeben, um die Aktivität der betreffenden Oxidoreduktasen zu verstärken (Enhancer) oder um bei stark unterschiedlichen Redoxpotentialen zwischen den oxidierenden Enzymen und den Anschmutzungen den Elektronenfluss zu gewährleisten (Mediatoren).If desired, 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. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
Die Enzyme können in jeder nach dem Stand der Technik etablierten Form eingesetzt werden. Hierzu gehören beispielsweise die durch Granulation, Extrusion oder Lyophilisierung erhaltenen festen Präparationen oder, insbesondere bei flüssigen oder gelförmigen Mitteln, Lösungen der Enzyme, vorteilhafterweise möglichst konzentriert, wasserarm und/oder mit Stabilisatoren versetzt. Alternativ können die Enzyme sowohl für die feste als auch für die flüssige Darreichungsform verkapselt werden, beispielsweise durch Sprühtrocknung oder Extrusion der Enzymlösung zusammen mit einem vorzugsweise natürlichen Polymer oder in Form von Kapseln, beispielsweise solchen, bei denen die Enzyme wie in einem erstarrten Gel eingeschlossen sind oder in solchen vom Kern-Schale-Typ, bei dem ein enzymhaltiger Kern mit einer Wasser-, Luft- und/oder Chemikalien-undurchlässigen Schutzschicht überzogen ist. In aufgelagerten Schichten können zusätzlich weitere Wirkstoffe, beispielsweise Stabilisatoren, Emulgatoren, Pigmente, Bleich- oder Farbstoffe aufgebracht werden. Derartige Kapseln werden nach an sich bekannten Methoden, beispielsweise durch Schüttel- oder Rollgranulation oder in Fluid-bed-Prozessen aufgebracht. Vorteilhafterweise sind derartige Granulate, beispielsweise durch Aufbringen polymerer Filmbildner, staubarm und aufgrund der Beschichtung lagerstabil. Weiterhin ist es möglich, zwei oder mehrere Enzyme zusammen zu konfektionieren, so dass ein einzelnes Granulat mehrere Enzymaktivitäten aufweist.The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers. Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating. Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.
Bevorzugt werden ein oder mehrere Enzyme und/oder Enzymzubereitungen, vorzugsweise Protease-Zubereitungen und/oder Amylase-Zubereitungen, in Mengen von 0,1 Gew.-% bis 5 Gew.-%, vorzugsweise von 0,2 Gew.-% bis 4,5 Gew.-% und insbesondere von 0,4 Gew.-% bis 4 Gew.-%, eingesetzt.Preference is given to one or more enzymes and / or enzyme preparations, preferably protease preparations and / or amylase preparations, in amounts of from 0.1% by weight to 5% by weight, preferably from 0.2% by weight to 4 , 5 wt .-% and in particular from 0.4 wt .-% to 4 wt .-%, used.
Als Parfümöle oder Duftstoffe können einzelne Riechstoffverbindungen, z.B. synthetische Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, zum Beispiel Pinien-, Citrus-, Jasmin-, Patchouly-, Rosen- oder Ylang-Ylang-Öl. Um wahrnehmbar zu sein, muss ein Riechstoff flüchtig sein, wobei neben der Natur der funktionellen Gruppen und der Struktur der chemischen Verbindung auch die Molmasse eine wichtige Rolle spielt. So besitzen die meisten Riechstoffe Molmassen bis etwa 200 g/mol, während Molmassen von 300 g/mol und darüber eher eine Ausnahme darstellen. Auf Grund der unterschiedlichen Flüchtigkeit von Riechstoffen verändert sich der Geruch eines aus mehreren Riechstoffen zusammengesetzten Parfüms oder Duftstoffs während des Verdampfens, wobei man die Geruchseindrücke in "Kopfnote" (top note), "Herz- oder Mittelnote" (middle note, body) sowie "Basisnote" (end note, dry out) unterteilt. Da die Geruchswahrnehmung zu einem großen Teil auch auf der Geruchsintensität beruht, besteht die Kopfnote eines Parfüms oder Duftstoffs nicht allein aus leichtflüchtigen Verbindungen, während die Basisnote zum größten Teil aus weniger flüchtigen, d.h. haftfesten Riechstoffen besteht. Bei der Komposition von Parfüms können leichter flüchtige Riechstoffe beispielsweise an bestimmte Fixative gebunden werden, wodurch ihr zu schnelles Verdampfen verhindert wird. Bei der nachfolgenden Einteilung der Riechstoffe in "leichter flüchtige" oder "haftfeste" Riechstoffe ist also über den Geruchseindruck und darüber, ob der entsprechende Riechstoff als Kopf- oder Herznote wahrgenommen wird, nichts ausgesagt. Die Duftstoffe können direkt verarbeitet werden, es kann aber auch vorteilhaft sein, die Duftstoffe auf Träger aufzubringen, die durch eine langsamere Duftfreisetzung für langanhaltenden Duft sorgen. Als solche Trägermaterialien haben sich beispielsweise Cyclodextrine bewährt, wobei die Cyclodextrin-Parfüm-Komplexe zusätzlich noch mit weiteren Hilfsstoffen beschichtet werden können.As perfume oils or fragrances, individual perfume compounds, for example synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. Thus, most fragrances have molecular weights up to about 200 g / mol, while molar masses of 300 g / mol and above are more of an exception. Due to the different volatility of fragrances, the odor of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note, body" as well as " Base note "(end note, dry out). Since odor perception is also largely based on odor intensity, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note is for the most part consists of less volatile, ie adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as the head or middle note, nothing said. The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
Bei der Wahl des Färbemittels muss beachtet werden, dass die Färbemittel eine hohe Lagerstabilität und Unempfindlichkeit gegenüber Licht sowie keine zu starke Affinität gegenüber textilen Oberflächen und hier insbesondere gegenüber Kunstfasern aufweisen können. Gleichzeitig ist auch zu berücksichtigen, dass Färbemittel unterschiedliche Stabilitäten gegenüber der Oxidation aufweisen können. Im Allgemeinen gilt, dass wasserunlösliche Färbemittel gegen Oxidation stabiler sind als wasserlösliche Färbemittel. Abhängig von der Löslichkeit und damit auch von der Oxidationsempfindlichkeit variiert die Konzentration des Färbemittels in den Wasch- oder Reinigungsmitteln. Bei gut wasserlöslichen Färbemitteln werden typischerweise Färbemittel-Konzentrationen im Bereich von einigen 10-2 Gew.-% bis 10-3 Gew.-% gewählt. Bei den auf Grund ihrer Brillanz insbesondere bevorzugten, allerdings weniger gut wasserlöslichen Pigmentfarbstoffen liegt die geeignete Konzentration des Färbemittels in Wasch- oder Reinigungsmitteln dagegen typischerweise bei einigen 10-3 Gew.-% bis 10-4 Gew.-%. Es werden Färbemittel bevorzugt, die im Waschprozess oxidativ zerstört werden können sowie Mischungen derselben mit geeigneten blauen Farbstoffen, sog. Blautönern. Es hat sich als vorteilhaft erwiesen, Färbemittel einzusetzen, die in Wasser oder bei Raumtemperatur in flüssigen organischen Substanzen löslich sind. Geeignet sind beispielsweise anionische Färbemittel, zum Beispiel anionische Nitrosofarbstoffe.When choosing the colorant, it must be taken into account that the colorants can have a high storage stability and insensitivity to light as well as not too high an affinity for textile surfaces and, in particular, for synthetic fibers. At the same time it should also be considered that colorants may have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 -2 % by weight to 10 -3 % by weight are typically selected. On the other hand, in the case of the pigment dyes preferred in particular because of their brilliance, but less readily water-soluble, the suitable concentration of the colorant in detergents or cleaners is typically from about 10 -3 % by weight to 10 -4 % by weight. Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
Zusätzlich zu den bisher genannten Komponenten können die Wasch- oder Reinigungsmittel weitere Inhaltsstoffe enthalten, welche die anwendungstechnischen und/oder ästhetischen Eigenschaften dieser Mittel weiter verbessern. Bevorzugte Mittel enthalten einen oder mehrere Stoffe aus der Gruppe der Elektrolyte, pH-Stellmittel, Fluoreszenzmittel, Hydrotrope, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, optische Aufheller, Vergrauungsinhibitoren, Einlaufverhinderer, Knitterschutzmittel, Farbübertragungsinhibitoren, antimikrobiellen Wirkstoffen, Germizide, Fungizide, Antioxidantien, Antistatika, Bügelhilfsmittel, Phobier- und Imprägniermittel, Quell- und Schiebefestmittel sowie UV-Absorber.In addition to the components mentioned so far, the detergents or cleaning agents may contain further ingredients which further improve the performance and / or aesthetic properties of these agents. Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.
Als Elektrolyte aus der Gruppe der anorganischen Salze kann eine breite Anzahl der verschiedensten Salze eingesetzt werden. Bevorzugte Kationen sind die Alkali- und Erdalkalimetalle, bevorzugte Anionen sind die Halogenide und Sulfate. Aus herstellungstechnischer Sicht ist der Einsatz von NaCl oder MgCl2 in den Wasch- oder Reinigungsmitteln bevorzugt.As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the washing or cleaning agents is preferred.
Um den pH-Wert von Wasch- oder Reinigungsmitteln in den gewünschten Bereich zu bringen, kann der Einsatz von pH-Stellmitteln angezeigt sein. Einsetzbar sind hier sämtliche bekannten Säuren oder Laugen, sofern sich ihr Einsatz nicht aus anwendungstechnischen oder ökologischen Gründen oder aus Gründen des Verbraucherschutzes verbietet. Üblicherweise überschreitet die Menge dieser Stellmittel 1 Gew.-% der Gesamtformulierung nicht.In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Applicable here are all known acids or alkalis, unless their use is prohibited for application or environmental reasons or for reasons of consumer protection. Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation.
Als Schauminhibitoren kommen Seifen, Öle, Fette, Paraffine oder Silikonöle in Betracht, die gegebenenfalls auf Trägermaterialien aufgebracht sein können. Als Trägermaterialien eignen sich beispielsweise anorganische Salze wie Carbonate oder Sulfate, Cellulosederivate oder Silikate sowie Mischungen der vorgenannten Materialien. Im Rahmen der vorliegenden Anmeldung bevorzugte Mittel enthalten Paraffine, vorzugsweise unverzweigte Paraffine (n-Paraffine) und/oder Silikone, vorzugsweise linear-polymere Silikone, welche nach dem Schema (R2SiO)x aufgebaut sind und auch als Silikonöle bezeichnet werden. Diese Silikonöle stellen gewöhnlich klare, farblose, neutrale, geruchsfreie, hydrophobe Flüssigkeiten mit einem Molekulargewicht zwischen 1000 g/mol und 150000 g/mol und Viskositäten zwischen 10 mPa·s und 1000000 mPa·s dar.Suitable foam inhibitors are soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. In the context of the present application preferred agents include 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. These silicone oils usually are clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1000 g / mol and 150000 g / mol and viscosities between 10 mPa.s and 1000000 mPa.s.
Als soil repellents kommen die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder Terephthalsäure und deren Derivate, insbesondere Polymere aus Ethylenterephthalat und/oder Polyethylenglycolterephthalat oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen, in Frage. Insbesondere bevorzugt von diesen sind die sulfonierten Derivate der Phthalsäure- und Terephthalsäure-Polymere.Suitable soil repellents are known from the prior art polymers of phthalic acid and / or terephthalic acid and derivatives thereof, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate or anionic and / or nonionic modified derivatives of these in question. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
Optische Aufheller können insbesondere den Waschmitteln zugesetzt werden, um Vergrauungen und Vergilbungen der behandelten Textilien zu beseitigen. Diese Stoffe ziehen auf die Faser auf und bewirken eine Aufhellung und vorgetäuschte Bleichwirkung, indem sie unsichtbare Ultraviolettstrahlung in sichtbares längerwelliges Licht umwandeln, wobei das aus dem Sonnenlicht absorbierte ultraviolette Licht als schwach bläuliche Fluoreszenz abgestrahlt wird und mit dem Gelbton der vergrauten oder vergilbten Wäsche reines Weiß ergibt. Geeignete Verbindungen stammen beispielsweise aus den Substanzklassen der 4,4'-Diamino-2,2'-stilbendisulfonsäuren (Flavonsäuren), 4,4'-Distyryl-biphenylen, Methylumbelliferone, Cumarine, Dihydrochinolinone, 1,3-Diarylpyrazoline, Naphthalsäureimide, Benzoxazol-, Benzisoxazol- und Benzimidazol-Systeme sowie der durch Heterocyclen substituierten Pyrenderivate.Optical brighteners may in particular be added to the detergents in order to eliminate graying and yellowing of the treated textiles. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence and the yellow color of the gray or yellowed wash pure white results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Wiederaufziehen des Schmutzes zu verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate verwenden, zum Beispiel abgebaute Stärke und Aldehydstärken. Auch Polyvinylpyrrolidon ist brauchbar. Als Vergrauungsinhibitoren einsetzbar sind weiterhin Celluloseether wie Carboxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxy-methylcellulose und deren Gemische. Besonders geeignet sind beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxypropylcellulose mit einem Anteil an Methoxygruppen von 15 bis 30 Gew.-% und an Hydroxypropylgruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether.Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations can be used, for example degraded starch and aldehyde starches. Polyvinylpyrrolidone is also useful. Also usable as graying inhibitors are cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof. Particularly suitable are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30 wt .-% and of hydroxypropyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether.
Da textile Flächengebilde, insbesondere aus Reyon, Zellwolle, Baumwolle und deren Mischungen, zum Knittern neigen können, weil die Einzelfasern gegen Durchbiegen, Knicken, Pressen und Quetschen quer zur Faserrichtung empfindlich sind, können synthetische Knitterschutzmittel eingesetzt werden. Hierzu zählen beispielsweise synthetische Produkte auf der Basis von Fettsäuren, Fettsäureestern, Fettsäureamiden, -alkylolestern, -alkylolamiden oder Fettalkoholen, die meist mit Ethylenoxid umgesetzt sind, oder Produkte auf der Basis von Lecithin oder modifizierter Phosphorsäureester.Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and crushing transversely to the fiber direction, 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 ester.
Phobier- und Imprägnierverfahren dienen der Ausrüstung von Textilien mit Substanzen, welche die Ablagerung von Schmutz verhindern oder dessen Auswaschbarkeit erleichtern. Bevorzugte Phobier- und Imprägniermittel sind perfluorierte Fettsäuren, auch in Form ihrer Aluminium- und Zirkoniumsalze, organische Silikate, Silikone, Polyacrylsäureester mit perfluorierter Alkohol-Komponente oder mit perfluoriertem Acyl- oder Sulfonyl-Rest gekoppelte, polymerisierbare Verbindungen. Auch Antistatika können enthalten sein. Die schmutzabweisende Ausrüstung mit Phobier- und Imprägniermitteln wird oft als eine Pflegeleicht-Ausrüstung eingestuft. Das Eindringen der Imprägniermittel in Form von Lösungen oder Emulsionen der betreffenden Wirkstoffe kann durch Zugabe von Netzmitteln erleichtert werden, welche die Oberflächenspannung herabsetzen. Ein weiteres Einsatzgebiet von Phobier- und Imprägniermitteln ist die wasserabweisende Ausrüstung von Textilwaren, Zelten, Planen, Leder usw., bei der im Gegensatz zum Wasserdichtmachen die Gewebeporen nicht verschlossen werden, der Stoff also atmungsaktiv bleibt (Hydrophobieren). Die zum Hydrophobieren verwendeten Hydrophobiermittel überziehen Textilien, Leder, Papier, Holz usw. mit einer sehr dünnen Schicht hydrophober Gruppen, wie längere Alkyl-Ketten oder Siloxan-Gruppen. Geeignete Hydrophobiermittel sind zum Beispiel Paraffine, Wachse, Metallseifen usw. mit Zusätzen an Aluminium- oder Zirkonium-Salzen, quartäre Ammonium-Verbindungen mit langkettigen AlkylResten, Harnstoff-Derivate, Fettsäure-modifizierte Melaminharze, Chrom-Komplexsalze, Silikone, Zinn-organische Verbindungen und Glutardialdehyd sowie perfluorierte Verbindungen. Die hydrophobierten Materialien fühlen sich nicht fettig an; dennoch perlen - ähnlich wie an gefetteten Stoffen - Wassertropfen an ihnen ab, ohne zu benetzen. So haben zum Beispiel Silikon-imprägnierte Textilien einen weichen Griff und sind wasser- und schmutzabweisend; Flecke aus Tinte, Wein, Fruchtsäften und dergleichen sind leichter zu entfernen.Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability. Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical coupled polymerizable compounds. Antistatic agents may also be included. The antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. A further field of application of repellents and impregnating agents is the water-repellent finish of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing). The water repellents used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are, for example, paraffins, waxes, metal soaps, etc. with additives on aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, tin-organic compounds and glutaric dialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening. For example, silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.
Zur Bekämpfung von Mikroorganismen können antimikrobielle Wirkstoffe eingesetzt werden. Hierbei unterscheidet man je nach antimikrobiellem Spektrum und Wirkungsmechanismus zwischen Bakteriostatika und Bakteriziden, Fungistatika und Fungiziden und so weiter. Stoffe aus diesen Gruppen sind beispielsweise Benzalkoniumchloride, Alkylarlylsulfonate, Halogenphenole und Phenolmercuriacetat, wobei auch gänzlich auf diese Verbindungen verzichtet werden kann.Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides and so on. Substances from these groups are, for example, benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercuriacetate, wherein it is also possible to dispense entirely with these compounds.
Um unerwünschte, durch Luftsauerstoffeinwirkung und andere oxidative Prozesse verursachte Veränderungen an den Waschmitteln und/oder den behandelten Textilien zu verhindern, können die Mittel Antioxidantien enthalten. Zu dieser Verbindungsklasse gehören beispielsweise substituierte Phenole, Hydrochinone, Brenzcatechine und aromatische Amine sowie organische Sulfide, Polysulfide, Dithiocarbamate, Phosphite und Phosphonate.To prevent undesirable changes to the detergents and / or the treated textiles caused by atmospheric oxygenation and other oxidative processes, the agents may 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.
Ein erhöhter Tragekomfort kann aus der zusätzlichen Verwendung von Antistatika resultieren. Antistatika vergrößern die Oberflächenleitfähigkeit und ermöglichen damit ein verbessertes Abfließen gebildeter Ladungen. Äußere Antistatika sind in der Regel Substanzen mit wenigstens einem hydrophilen Molekülliganden und geben auf den Oberflächen einen mehr oder minder hygroskopischen Film. Diese zumeist grenzflächenaktiven Antistatika lassen sich in stickstoffhaltige (Amine, Amide, quartäre Ammoniumverbindungen), phosphorhaltige (Phosphorsäureester) und schwefelhaltige (Alkylsulfonate, Alkylsulfate) Antistatika unterteilen. Lauryl- (oder Stearyl-) dimethylbenzylammoniumchloride eignen sich ebenfalls als Antistatika für Textilien und als Zusatz zu Waschmitteln, wobei zusätzlich ein Avivageeffekt erzielt wird.Increased comfort may result from the additional use of antistatic agents. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided 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 antistatics for textiles and as an additive to detergents, wherein additionally a softening effect is achieved.
Zur Verbesserung des Wasserabsorptionsvermögens, der Wiederbenetzbarkeit der behandelten Textilien und zur Erleichterung des Bügelns der behandelten Textilien können in Textilwaschmitteln Silikonderivate eingesetzt werden. Diese verbessern zusätzlich das Ausspülverhalten von Wasch- oder Reinigungsmitteln durch ihre schauminhibierenden Eigenschaften. Bevorzugte Silikonderivate sind beispielsweise Polydialkyl- oder Alkylarylsiloxane, bei denen die Alkylgruppen ein bis fünf C-Atome aufweisen und ganz oder teilweise fluoriert sind. Bevorzugte Silikone sind Polydimethylsiloxane, die gegebenenfalls derivatisiert sein können und dann aminofunktionell oder quaterniert sind oder Si-OH-, Si-H- und/oder Si-Cl-Bindungen aufweisen. Weitere bevorzugte Silikone sind die Polyalkylenoxid-modifizierten Polysiloxane, also Polysiloxane, welche beispielsweise Polyethylenglykole aufweisen, sowie die Polyalkylenoxid-modifizierten Dimethylpolysiloxane.To improve the water absorbency, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, silicone derivatives can be used in laundry detergents. These additionally improve the rinsing out of detergents or cleaning agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or Si-OH, Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols, and the polyalkylene oxide-modified dimethylpolysiloxanes.
Schließlich können auch UV-Absorber eingesetzt werden, die auf die behandelten Textilien aufziehen und die Lichtbeständigkeit der Fasern verbessern. Verbindungen, die diese gewünschten Eigenschaften aufweisen, sind beispielsweise die durch strahlungslose Desaktivierung wirksamen Verbindungen und Derivate des Benzophenons mit Substituenten in 2- und/oder 4-Stellung. Weiterhin sind auch substituierte Benzotriazole, in 3-Stellung phenylsubstituierte Acrylate (Zimtsäurederivate), gegebenenfalls mit Cyanogruppen in 2-Stellung, Salicylate, organische Ni-Komplexe sowie Naturstoffe wie Umbelliferon und die körpereigene Urocansäure geeignet.Finally, it is also possible to use UV absorbers which are applied to the treated textiles and improve the light resistance of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, 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.
Proteinhydrolysate sind auf Grund ihrer faserpflegenden Wirkung weitere geeignete Aktivsubstanzen. Proteinhydrolysate sind Produktgemische, die durch sauer, basisch oder enzymatisch katalysierten Abbau von Proteinen (Eiweißen) erhalten werden. Proteinhydrolysate sowohl pflanzlichen als auch tierischen Ursprungs können eingesetzt werden. Tierische Proteinhydrolysate sind beispielsweise Elastin-, Kollagen-, Keratin-, Seiden- und Milcheiweiß-Proteinhydrolysate, die auch in Form von Salzen vorliegen können. Bevorzugt ist die Verwendung von Proteinhydrolysaten pflanzlichen Ursprungs, zum Beispiel Soja-, Mandel-, Reis-, Erbsen-, Kartoffel- und Weizenproteinhydrolysate. Wenngleich der Einsatz der Proteinhydrolysate als solche bevorzugt ist, können an deren Stelle gegebenenfalls auch anderweitig erhaltene Aminosäuregemische oder einzelne Aminosäuren wie beispielsweise Arginin, Lysin, Histidin oder Pyroglutaminsäure eingesetzt werden. Ebenfalls möglich ist der Einsatz von Derivaten der Proteinhydrolysate, beispielsweise in Form ihrer Fettsäure-Kondensationsprodukte.Protein hydrolyzates are due to their fiber-care effect other suitable active substances. Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). Protein hydrolysates of both vegetable and animal origin can be used. Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Preference is given to the use of protein hydrolysates of plant origin, for example soybean, almond, rice, pea, potato and wheat protein hydrolysates. Although the use of the protein hydrolyzates is preferred as such, other amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.
Es wurden Waschversuche bei 40°C mit den in Tabelle 1 angegebenen standardisierten Anschmutzungen auf Baumwolle unter Einsatz eines bleichmittelfreien Flüssigwaschmittels V1 (Dosierung 69 g auf 17 l Wasser von 16 °dH) und einer Mischung M1 aus Waschmittel V1 und 8-Hydroxy-5-chinolinsulfonsäure (Verbindung A)
(Dosierung 69 g V1 und 1 g A auf 17 l Wasser von 16 °dH) durchgeführt. Nach Trocknung der Baumwoll-Lappen wurde deren Helligkeit mit Hilfe der Farbabstandsmessung gemäß der L*a*b*-Werte und der daraus berechneten Y-Werte als Maß für die Helligkeit bestimmt. Tabelle 1 zeigt die Unterschiede der Differenzwerte dY, die sich aus der Differenz Y(nach dem Waschen) - Y (vor dem Waschen) zwischen M1 und V1 ergaben.
Die Helligkeitsdifferenzen bei Einsatz der erfindungswesentlichen Substanz waren signifikant größer als diejenigen, die sich beim Einsatz des von der Substanz freien Vergleichswaschmittels ergeben, was einem höheren Weißgrad und somit einer verbesserten Fleckentfernung entspricht.The brightness differences when using the substance essential to the invention were significantly greater than those resulting from the use of the substance-free comparative detergent, which corresponds to a higher whiteness and thus improved stain removal.
Claims (9)
- The use of compounds of general formula (I),in which R1, R2, R3, R4, R5 and R6 represent, independently of one another, hydrogen or SO3X, with the proviso that at least 1 of the mentioned functional groups R1 to R6 is not hydrogen, and X represents hydrogen, an alkali metal or ammonium,in liquid laundry detergents containing builders and no oxidative bleaching agents to improve the washing or cleaning performance against bleachable stains.
- The use according to claim 1, characterized in that the stains contain polymerizable substances, selected from polyphenolic dyes, in particular flavonoids, more particularly dyes from the class of anthocyanidins or anthocyanins or oligomers, of said compounds.
- The use according to claim 1 or 2, characterized in that the improved washing or cleaning performance consists in improved removal of green, yellow, red, blue, violet, lilac, brown, purple or pink stains, in particular marks from grass, fruits or vegetables, in particular stains caused by food products, such as spices, sauces, chutneys, curries, purees and jams, or beverages, such as coffee, tea, wines and juices, which contain corresponding green, yellow, red, violet, lilac, brown, purple, pink and/or blue dyes.
- The use according to one of claims 1 to 3, characterized in that the stains are selected from stains caused by cherries, morellos, grapes, apples, pomegranates, chokeberries, plums, sea buckthorns, acai berries, kiwis, mangoes, grass or berries, in particular caused by redcurrants, blackcurrants, elderberries, blackberries, raspberries, blueberries, lingonberries, cranberries, strawberries or bilberries, or by coffee, tea, red cabbage, blood orange, eggplant, tomato, carrot, beetroot, spinach, bell pepper, red or blue potato or red onion.
- A liquid laundry detergent, which does not contain any oxidative bleaching agent, containing builders and a compound of general formula (I),
- The detergent according to claim 5, characterized in that it contains 0.01 wt.% to 10 wt.%, in particular 0.05 wt.% to 5 wt.% of a compound of general formula (I).
- The detergent according to claim 5 or 6, characterized in that it contains, in addition to the compound of general formula (I), further constituents of laundry detergents, selected from the group of surfactants.
- The use according to one of claims 1 to 4 or the detergent according to one of claims 5 to 7, characterized in that, in the compounds of general formula (I), 1 to 4, in particular 1 to 2, SO3X substituents are contained.
- The use or the detergent according to one of the preceding claims, characterized in that, in the compound of formula I, R4 is a SO3X substituent.
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US5380458A (en) * | 1992-10-02 | 1995-01-10 | Colgate-Palmolive Co. | Stabilized hypohalite compositions |
EP1255806B1 (en) * | 2000-02-14 | 2006-09-27 | The Procter & Gamble Company | Stable, aqueous compositions for treating surfaces, especially fabrics |
GB2372750B (en) * | 2001-01-18 | 2004-09-08 | Avecia Ltd | Hexa co-ordinated metal complexes of monoazo dyes for use in inks suitable for ink jet printing |
US7557076B2 (en) * | 2002-06-06 | 2009-07-07 | The Procter & Gamble Company | Organic catalyst with enhanced enzyme compatibility |
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KRYSTYNA. SOROKA, RATHNAPALA S. VITHANAGE, DENISE A. PHILLIPS, BRIAN. WALKER, AND PURNENDU K. DASGUPTA: "Fluorescence properties of metal complexes of 8-hydroxyquinoline-5-sulfonic acid and chromatographic applications", ANAL. CHEM., vol. 59, no. 4, February 1987 (1987-02-01), pages 629 - 636, Retrieved from the Internet <URL:https://cdn-pubs.acs.org/doi/pdf/10.1021/ac00131a019> [retrieved on 20180704], DOI: 10.1021/ac00131a019 * |
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