EP1433839A1 - Compositions de lavage et nettoyage optimisées pour un effet amélioré de blanchiment à basse température - Google Patents

Compositions de lavage et nettoyage optimisées pour un effet amélioré de blanchiment à basse température Download PDF

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EP1433839A1
EP1433839A1 EP02028958A EP02028958A EP1433839A1 EP 1433839 A1 EP1433839 A1 EP 1433839A1 EP 02028958 A EP02028958 A EP 02028958A EP 02028958 A EP02028958 A EP 02028958A EP 1433839 A1 EP1433839 A1 EP 1433839A1
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Prior art keywords
acid
detergent
taed
cleaning agent
acids
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German (de)
English (en)
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EP1433839B1 (fr
EP1433839B2 (fr
Inventor
Elke Dr. Philippsen-Neu
Bernhard Enders
Jürgen Krichel
Claudia Adriany
Michaela Gajewski
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Dalli Werke GmbH and Co KG
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Dalli Werke GmbH and Co KG
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Priority to EP02028958.3A priority Critical patent/EP1433839B2/fr
Priority to DK02028958.3T priority patent/DK1433839T4/da
Priority to DE50210897T priority patent/DE50210897D1/de
Priority to AT02028958T priority patent/ATE373073T1/de
Priority to ES02028958.3T priority patent/ES2290242T5/es
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Publication of EP1433839A1 publication Critical patent/EP1433839A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds

Definitions

  • the present invention relates to a composition for washing or Detergents that have a bleaching effect at low temperatures to have.
  • Textile detergent formulations as powder and as pressed molded articles usually contain a bleaching system, which mostly consists of Peroxy compounds, peracids or mixtures which provide active oxygen consists of it and bleach activators.
  • a bleaching system which mostly consists of Peroxy compounds, peracids or mixtures which provide active oxygen consists of it and bleach activators.
  • the most used Bleach activator is tetraacetylethylene diamine ("TAED").
  • TAED tetraacetylethylene diamine
  • bleach activators are also known from the prior art. So describes e.g. B. DE 100 38 844 A1 a cationic bleach activator containing detergent and cleaning agent, this cationic Bleach activator an acetonitrile derivative with the anion of Is cumene sulfonic acid.
  • this bleach activator By adding this bleach activator in this application the bleaching effect of aqueous peroxide liquors so far be increased that even at temperatures below 60 ° C in Essentially the same effect as with the peroxide liquor alone 95 ° C can be reached.
  • the registration also describes the simultaneous use of the acetonitrile derivative with an enzyme Increasing the cleaning performance of the detergent and cleaning agent, especially compared to protein-containing, starch-containing and / or colored stains, for use in aqueous washing and Cleaning solutions containing a peroxygen compound.
  • Enzymes are described in particular those enzymes that have a pH optimum preferably in the alkaline range up to about pH 10. A special bleaching effect at low temperatures is described in this application not considered.
  • EP 0 941 299 describes a textile detergent formulation which is used as Bleach activators contains quaternized glycine nitriles, moreover Bleach, surfactants and a calcium and / or magnesium sequestering connection with builder or cobuilder function in certain relationships to each other.
  • this detergent composition will have an improved bleaching effect at low Washing temperatures (from 20 ° C to 60 ° C) achieved, especially at Use this detergent formulation with hard water.
  • EP 0 778 832 is concerned with a method of manufacture such quaternized glycine nitriles, which act as a bleach activator in Detergent compositions can be used.
  • the object of the present invention was to provide a washing and Provide detergent composition at low Temperatures (below 45 ° C) a good washing and bleaching performance developed.
  • a detergent composition containing at least one bleach activator and at least one TAED with slow peracetic acid release kinetics.
  • All bleach activators can be used as bleach activators that show an activating effect for the bleaching agent in washing liquors at temperatures below 45 ° C.
  • These are, for example, compounds of the substance classes of polyacylated sugar or sugar derivatives with C 1 -C 10 -acyl radicals, preferably acetyl, Propionyl, octanoyl, nonanoyl or benzoyl residues, especially acetyl residues.
  • Mono- or disaccharides and their reduced or oxidized derivatives can be used as sugar or sugar derivatives, preferably glucose, mannose, fructose, sucrose, xylose or lactose.
  • bleach activators of this class of substances are, for example, pentaacetylglucose, xylose tetraacetate, 1-benzoyl-2,3,4,6-tetraacetylglucose and 1-octanoyl-2,3,4,6-tetraacetylglucose.
  • 0-Acyloxime esters such as z. B. 0-acetylactone oxime, 0-benzoylacetone oxime, bis (propylimino) carbonate or bis (cyclohexylimino) carbonate.
  • acylated oximes and Oxime esters are described, for example, in EP-A-028 432 and EP-A-267 046.
  • N-acylcaprolactams such as for example N-acetylcaprolactam, N-benzoylcaprolactam, N-octanoylcaprolactam, N-octanoylcaprolactam or carbonyl biscaprolactam.
  • bleach activators are 2-alkyl- or 2-aryl- (4H) -3,1-benzoxain-4-ones, as for example in EP-B-332 294 and EP-B-502 013.
  • 2-phenyl- (4H) -3,1-benzoxain-4-one and 2-methyl- (4H) -3,1-benzoxain-4-one can be used.
  • bleach activators from the N or O-acyl compounds for example multi-acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular Tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, Hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, Carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, Sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as Pentaacetyl glucose can be used.
  • multi-acylated alkylenediamines in particular tetraacetylethylenediamine
  • acylated glycolurils in particular Tetraacetylglycoluril
  • European patent application EP 0 464 880 discloses bleach-boosting cationic nitriles of the general formula R'R ", R""N + -CR 1 R 2 -CNX - in which R 1 and R 2 are hydrogen or a substituent with at least one a C atom, R 'is a C 1 -C 24 alkyl, alkenyl or alkyl ether group or a group -CR 1 R 2 -CN, and R''andR''' each have a C 1 -C 24 alkyl - or hydroxyalkyl group and the counter anion X - is an organic sulfonate, or a carboxylate.
  • connections can be used, as in the DE 100 38 844 A1 are described under the general formula I.
  • a preferred bleach activator is a quaternized one Glycine nitrile from the group N-methylmorpholinium acetonitrile methyl sulfate, sulfate and hydrogen sulfate.
  • the preferred activator can as the only bleach activator in the detergent composition be used, or in combination with one of the aforementioned Bleach activators.
  • a combination of one quaternized glycine nitrile with TAED is a quaternized glycine nitrile TAED used in a ratio of 4: 1 to 1: 4.
  • a ratio of TAED to Glycine nitrile of 4: 1, 3: 1 and 3: 2 is particularly suitable for textile detergents.
  • washing and cleaning performance of the agent according to the invention clearly can improve if for use at low temperatures (below 45 ° C) a TAED is used in a processing form that has a delayed release of peracetic acid.
  • a TAED assembled in this way is used that does not immediately in contact with water in combination with percarbonate Peracetic acid releases, but only with a certain delay.
  • the delayed release of peracetic acid increases the washing performance other ingredients, especially at a washing temperature from 30 ° C.
  • the improved washing performance is due to the fact that At the beginning of the washing process, the bleach activator used Effect comes from the rapid release of peracetic acid performance seems to be disturbed by the TAED. This means, that the bleach activator shows a significantly better effect if too No very high peracetic acid concentration at the beginning of the washing process is present. The same applies to the performance of Properase. After the Bleach activator has its effect, it is beneficial for that Washing result if the Peracetic acid concentration increased. Such a "delayed" occurrence a high peracetic acid concentration improves in particular Bleaching action of the washing or cleaning agent according to the invention low temperatures.
  • a TAED with a protective cover is preferably used coated (coated), which dissolves only slowly in the wash liquor, and thus the TAED comes into effect only after a delay, namely if that Coating is removed.
  • the thickness of the coating also influences the speed with that the TAED can come into effect. The thicker the coating, the more it takes longer until the coating in the wash liquor is so far away is that the TAED can be effective.
  • a concentration of less than 100 mg / l are understood to mean a “high Peracetic acid concentration "a concentration of more than 300 mg / l.
  • Delayed release means that a Concentration of more than 100 mg / l peracetic acid in the wash liquor only after a few minutes, preferably after at least 5 minutes and especially preferably occurs after at least 8 min. After that time is then a rapid increase in the concentration of peracetic acid in the wash liquor he wishes.
  • TAED's with a delayed or slow peracetic acid release kinetics are commercially available.
  • the detergent composition suitable bleaching agents are added, which are customary, generally known Can be bleach for detergent compositions.
  • Suitable peroxygen compounds for use in agents according to the invention are, in particular, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the washing conditions, to which alkali metal perborates such as, for. B. sodium perborate tetrahydrate and sodium perborate monohydrate, further include alkali metal carbonate perhydrates such as sodium carbonate perhydrate ("sodium percarbonate”) and -persilicates and / or -persulfates such as caroate.
  • the bleaching system of the detergent formulation can contain inorganic or organic peracids, especially percarboxylic acids, e.g. B.
  • C 1 -C 12 percarboxylic acids C 8 -C 16 dipercarboxylic acids, imidopercaproic acids or aryldipercaproic acids.
  • Preferred examples of usable acids are peracetic acid, perbenzoic acid, linear or branched octanoic, nonanoic, decanoic or dodecane monoperacids, decanoic and dodecane diper acid, mono- and diperphthalic acids, isophthalic acids and terephthalic acids, phthalimidopercaproic acid, terephthaloyl diamide peroxapaponic acid (PAP).
  • percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • a particularly preferred peracid used is the peracid available under the trade name Eureco® (Ausimont, Italy).
  • Peroxygen compounds are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight and particularly preferably from 8% by weight to 25% by weight.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates
  • magnesium salts such as magnesium sulfate
  • At least a bleach activator and an effective peracid as raw materials side by side in the detergent or cleaning agent formulation, your Effect is time shifted against each other by the peracid delayed effect.
  • the peracid is preferably in granular form Form before.
  • This embodiment has the advantage that regardless of that pH set in the wash liquor and the wash temperature in each If there is a bleaching effect. At low pH (pH 8.5 to 9) occurs especially the effect of peracid in the foreground without Activation develops a bleaching effect. At higher pH (pH> 9) the bleach activator unfolds its full effect, so that here too there is an increased bleaching effect.
  • Quaternized imines or are usually used as bleaching catalysts Sulfonimines used, as described for example in US-A-5,360,568, US-A-5,360,569 and EP-A-453 003 are described, as well as manganese complexes, as described for example in WO-A 94/21777. Further Metal-containing bleaching catalysts which can be used are described in EP-A-458 397, EP-A-458 398 and EP-A-549 272. Bleaching catalysts are used in generally in amounts of up to 1% by weight, in particular 0.01 to 0.5% by weight, based on the detergent formulation.
  • Bleach stabilizers are additives that interfere with bleaching Traces of heavy metals can adsorb, bind or complex.
  • common complexing agents such as Ethylenediaminetetraacetate, nitrilotriacetic acid, methylglycinediacetic acid, ⁇ -alaninediacetic acid, ethylenediamine-N, N'-disuccinate and phosphonates such as ethylenediaminetetramethylenephosphonate, diethylenetriaminepentamethylenephosphonate or hydroxyethylidene-1,1-diphosphonic acid in the form of Acids or as partially or fully neutralized Alkali metal salts in amounts of up to 1% by weight, in particular 0.01 to 0.5% by weight, based on the detergent formulation.
  • a washing or cleaning agent according to the invention preferably contains 0.001 mg to 0.5 mg, in particular 0.02 mg to 0.3 mg of enzymatic active protein per gram of total agent.
  • the protein concentration can be made using known methods, e.g. B. the bicinchonic acid process (BCA method, Pierce Chemical Co., Rockford, IL) or the biuret method (A.G. Gornall, C.S. Bardawill and M.M. David, J. Biol. Chem. 177, 751-766, 1948).
  • a protease is used as at least one wash-active enzyme at temperatures below 45 ° C an essential part of their activity developed.
  • An example of such a protease is the enzyme Properase® 4000 E, distributed by Genencor International becomes.
  • the other enzymes used can also be those which are a Have maximum activity at low temperatures.
  • the used Enzymes should, however, at least at temperatures below 45 ° C Develop activity, even if the maximum does not have to be there.
  • enzymes commonly used in previous detergents are used, such as proteases, lipases, amylases, Cellulases and peroxidases.
  • enzymes effective in the alkaline medium in the usual amounts (about 0.1 to 3 wt .-%) used.
  • Proteases that can be used include those from microorganisms, especially bacteria or fungi, extractable enzymes with a pH optimum in the alkaline range, for example those from the international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or the European patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases.
  • Protease is preferably in such amounts in the agent according to the invention used that the finished agent 100 PE / g (protease units per Gram, determined according to that described in Tenside 7, 125 (1970) Method), in particular 125 PE / g to 5,000 PE / g and particularly preferred 150 PE / g to 4,500 PE / g.
  • Suitable proteases are commercially available available, for example under the names Alcalase®, Alkolase®, BLAP®, Durazym®, Esperase®, Everlase (RE), FN-Base®, Maxatase®, Maxaclean®, Maxacal®, Maxapem®, Optimase®, Optimax®, Opticlean®, Ovozyme®, Properase® Purafect®, Purafect®OxP or Savinase®. Of the above The use of Properase® is particularly preferred for proteases.
  • amylases which can be used in agents according to the invention which preferably in combination with at least one further enzyme Are used include those that can be obtained from bacteria or fungi Enzymes that have a pH optimum, preferably in the alkaline range have about pH 10.
  • Useful commercial products are, for example Amylase-LT, Aquazym®, Duramyl®, Maxamyl®, Purastar®, Purafect® OxAm or Termamyl®.
  • Amylase is preferably in the agent according to the invention in such amounts that the finished agent 0.01 KNU / g to 2 KNU / g ("Kilo Novo Units" per gram according to the company's standard method Novo, where 1 KNU is the amount of enzyme, the 5.26 g starch at pH 5.6 and 37 ° C, based on that of P. Bernfeld in S.P. Colowick and N.D. Kaplan, Methods in Enzymology, Volume 1, 1955, page 149 described method), in particular 0.015 KNU / g to 1.8 KNU / g and particularly preferably 0.03 KNU / g to 1.6 KNU / g. If that means according to the invention contains an amylase, this is preferred selected from the genetically modified amylases. Genetically modified amylases are, for example, from the international Patent applications WO 94/18314 or WO 95/21247 known.
  • the lipase optionally contained in the agent according to the invention is one of microorganisms, in particular bacteria or Mushrooms, extractable enzyme.
  • microorganisms in particular bacteria or Mushrooms
  • extractable enzyme for example from the European patent applications EP 0 204 208, EP 0 214 761, EP 0 258 068, EP 0 385 401, EP 0 407 225, EP 0 571 982 or the international Patent applications WO 87/00859 or WO 90/10695 known.
  • Lipase is used in Agents according to the invention preferably used in such amounts that the finished agent has a lipolytic activity in the range of 10 LU / g up to 10,000 LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tributyrin at 30 ° C and pH 7 after the in Method mentioned in EP 258 068), in particular 80 LU / g to 5,000 LU / g and particularly preferably 100 LU / g to 1,000 LU / g.
  • commercial Lipases are, for example, Lipex®, Lipolase®, Lipolase Ultra®, Lipomax®, Lipoprime®, Lipozym® and Lumafast®,
  • the cellulase usable according to the invention also belongs to the group Bacteria or fungi are extractable enzymes, which have a pH optimum preferably in the almost neutral to weakly alkaline pH range of 6 up to 9.5.
  • Such cellulases are for example from the German published documents DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950, the European patent applications EP 265 832, EP 269 977, EP 270 974, EP 0273 125 and EP 339 550 or international patent applications WO 96/34108 and WO 97/34005 known.
  • the finished agent are cellulolytic Activity from 0.05 IU / g to 1.5 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na-carboxymethyl cellulose at pH 9.0 and 40 ° C, as in Agric, Biol. Chem. 53, 1275 (1989) by S.Ito et al. described), in particular 0.07 IU / g to 1.4 IU / g and particularly preferably 0.1 IU / G to 1.3 IU / g.
  • Suitable commercial products are for example Carezyme®, Celluzyme®, Ecostase®, and Novozym® des Manufacturer Novo Nordisk or KAC® from Kao.
  • preferred Cellulases also include those from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase from the international patent application WO 97/14804 is known. It has one as described there Molecular weight of about 20 kDa and shows at 50 ° C in the pH range of 4 to 9 at least 80% of their maximum activity, with almost 50 % of maximum activity is maintained at pH 10.
  • You can like also described there, can be isolated from Melanocarpus albomyces and in genetically engineered Trichoderma reseei transformants to be produced.
  • Enzymes that can also be used in the compositions come from Class of cutinases, pullulanases, hemicellulases, oxidases, laccases and peroxidases and mixtures thereof. Are particularly suitable from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus obtained enzymatic Agents.
  • the enzymes can, e.g. B.
  • adsorbed on carriers and / or in Enveloping substances can be embedded to prevent them from premature inactivation to protect. They are in the washing or Detergents preferably in amounts up to 5 wt .-%, in particular from 0.2% by weight to 4% by weight.
  • the washing or cleaning agents according to the invention a mixture of two Proteases, one of which is Properase®, may be used in addition to other enzymes (amylase, lipase, cellulase).
  • Properase® along with another protease improves washing and Cleaning property of the washing and cleaning agent according to the invention clearly, while at the same time less total amount of protease must be used, both with regard to the used absolute amount, as well as with regard to the international used Enzyme units of the enzymes. This also leads to a Cost reduction in the production of the manufactured product.
  • Another benefit of reducing the total amount of protease is that a textile detergent produced in this way is particularly gentle on Woolen laundry works.
  • surfactants can be and detergent composition may be included, in particular nonionic and / or anionic surfactants or mixtures are preferred thereof.
  • Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18, carbon atoms, e.g. B. C 9 -C 11 alcohol sulfates, C 12 -C 13 alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • Suitable anionic surfactants are sulfated ethoxylated C 8 -C 22 alcohols (alkyl ether sulfates) or their soluble salts.
  • Compounds of this type are prepared, for example, by firstly using a C 8 -C 22 , preferably a C 10 -C 18 alcohol, e.g. B. a fatty alcohol, alkoxylated and the alkoxylation product then sulfated.
  • Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol.
  • the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide.
  • alkoxylated C 8 -C 22 alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide.
  • the alkoxylated C 8 -C 22 alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.
  • alkanesulfonates such as C 8 -C 24 , preferably C 10 -C 18 alkanesulfonates, and soaps such as the salts of C 8 -C 24 carboxylic acids.
  • anionic surfactants are C 9 -C 20 linear alkylbenzenesulfonates (LAS).
  • N-acyl sarcosinates with aliphatic saturated or unsaturated C 8 -C 25 acyl radicals, preferably C 10 -C 20 acyl radicals, e.g. B. N-oleoyl sarcosinate.
  • the anionic surfactants are preferred to the detergent formulation added in the form of salts. Suitable cations in these salts are Alkali metal ions such as sodium, potassium and lithium and ammonium ions such as z. B. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium ions.
  • anionic surfactants are linear alkylbenzenesulfonates and fatty alcohol sulfates of particular interest.
  • nonionic surfactants are alkoxylated C 8 -C 22 alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates.
  • the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant.
  • block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution.
  • 2 to 50, preferably 3 to 20 mol of at least one alkylene oxide are used per mol of alcohol.
  • Preferably used as the alkylene oxide is ethylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • nonionic surfactants are alkylphenol ethoxylates with C 6 -C 14 alkyl chains and 5 to 30 moles of ethylene oxide units.
  • alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5 Glucoside.
  • N-alkyl glucamides of general structure II or III
  • R 6 is C 6 -C 22 alkyl
  • R 8 is a polyhydroxyalkyl radical having 5 to 12 carbon atoms and at least 3 hydroxy groups.
  • R 6 is preferably C 10 -C 18 alkyl
  • R 7 is methyl
  • R 8 is a C 5 -C 6 radical.
  • such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C 10 -C 18 carboxylic acids.
  • the textile detergent formulation according to the invention preferably contains, as nonionic surfactants, ethoxylated C 10 -C 16 alcohols with 3 to 12 moles of ethylene oxide, in particular ethoxylated fatty alcohols and / or ethoxylated oxo alcohols.
  • substances with primarily builder or cobuilder function preferably representatives from the group of zeolites, silicates, Alkali metal phosphates, polycarboxylates and aminopolycarboxylates individually or used in mixtures.
  • zeolites and silicates can be used as inorganic Ion exchangers are called.
  • Suitable zeolites are in particular those of the types A, P, X, B, HS and MAP in their Sodium form or in forms in which sodium is partially against others Cations such as Li, K, Ca, Mg or ammonium are exchanged.
  • Cations such as Li, K, Ca, Mg or ammonium are exchanged.
  • Zeolites are described, for example, in EP-A 0 038 591, EP-A 0 087 035, US-A 4,604,224, GB-A 2 013 259, EP-A 0 522 726, EP-A 0 384 070 and WO-A 94/24251.
  • Suitable amorphous or crystalline silicates are primarily amorphous disilicates and crystalline ones Disilicates such as the layered silicate SKS-6 (manufacturer Hoechst).
  • the Silicates can be in the form of their alkali metal, alkaline earth metal or Ammonium salts are used. Na, Li and Mg silicates are preferred used.
  • Trisodium polyphosphate is particularly suitable as the alkali metal phosphate Consideration, which is also regarded as an inorganic ion exchanger can be.
  • Suitable unsaturated C 4 -C 8 dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.
  • Group (i) includes monoethylenically unsaturated C 3 -C 8 monocarboxylic acids such as. As acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.
  • Group (ii) includes monoethylenically unsaturated C 2 -C 22 olefins, vinyl alkyl ethers with C 1 -C 8 alkyl groups, styrene, vinyl esters of C 1 -C 8 carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C 2 -C 6 -olefins, vinyl alkyl ether with C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate.
  • Group (iii) includes (meth) acrylic esters of C 1 -C 8 alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 amines, N-vinylformamide and vinylimidazole.
  • polymers of group (ii) polymerize vinyl esters contain, they can also partially or completely to vinyl alcohol structural units be hydrolyzed.
  • Suitable copolymers and terpolymers are known for example from US-A 3,887,806 and DE-A 43 13 909.
  • Graft polymers of unsaturated carboxylic acids on low molecular weight Carbohydrates or hydrogenated carbohydrates, cf. US-A 5,227,446, DE-A 44 15 623 and DE-A 43 13 909 are also suitable.
  • suitable unsaturated carboxylic acids include maleic acid, Fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, Crotonic acid and vinyl acetic acid as well as mixtures of acrylic acid and Maleic acid in amounts of 40 to 95 wt .-%, based on the grafting component to be grafted on.
  • Suitable modifying monomers are above-mentioned monomers of groups (ii) and (iii).
  • Degraded polysaccharides such as e.g. B. acidic or enzymatically degraded starches, inulins or cellulose, reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such.
  • B. mannitol, sorbitol, aminosorbitol and glucamine and polyalkylene glycols with molecular weights up to M w 5,000 such as.
  • Grafted mined or mined from this group are preferred reduced starches and grafted polyethylene oxides, 20 up to 80% by weight of monomers based on the graft component in the Graft polymerization can be used.
  • grafting is preferred a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 used until 10:90.
  • Polyglyoxylic acids are described, for example, in EP-B 0 001 004, US-A 5,399,286, DE-A 41 06 355 and EP-A 0 656 914.
  • the end groups of Polyglyoxylic acids can have different structures.
  • polyamidocarboxylic acids and modified polyamidocarboxylic acids for example known from EP-A 0 454 126, EP-B 0 511 037, WO-A 94/01486 and EP-A 0 581 452.
  • the aminopolycarboxylates used are preferably also polyaspartic acid or cocondensates of aspartic acid with further amino acids, C 4 -C 25 mono- or dicarboxylic acids and / or C 4 -C 25 mono- or diamines.
  • C 4 -C 25 mono- or dicarboxylic acids and / or C 4 -C 25 mono- or diamines are particularly preferred in phosphorus-containing acids used prepared with C 6 -C 22 -mono- or -dicarboxylic acids or with C 6 -C 22 -mono- or -diamines.
  • Condensation products of citric acid with hydroxycarboxylic acids or Polyhydroxy compounds are e.g. B. known from WO-A 93/22362 and WO-A 92/16493.
  • Such condensates containing carboxyl groups usually molecular weights up to 10,000, preferably up to 5,000.
  • the textile detergent formulation according to the invention of the substance classes mentioned zeolite A, zeolite P, zeolite X, layered silicates such as SKS-6, trisodium polyphosphate, Acrylic acid / maleic acid copolymers (especially those of molecular weight 10,000 to 100,000), polyaspartic acid, citric acid, nitrilotriacetic acid, Methylglycinediacetic acid and mixtures thereof used.
  • zeolites and Polyaspartic acid zeolites and oligomaleic acids
  • zeolites and Acrylic acid / maleic acid copolymers trisodium polyphosphate and layered silicates, Trisodium polyphosphate and acrylic acid / maleic copolymers, Zeolites and trisodium polyphosphate as well as from zeolites, layered silicates and acrylic acid / maleic acid copolymers.
  • the textile detergent according to the invention can be used as an additional component formulation usual graying inhibitors and / or soil release polymers in the usual amounts for this (about 0.1 to 2% by weight) contain.
  • polyesters are known, for example from US-A 3,557,039, GB-A 1 154 730, EP-A-185 427, EP-A-421 984, EP-A-241 985, EP-A-272 033 and US-A 5,142,020.
  • soil release polymers are amphiphilic graft or Copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US-A 4,746,456, US-A 4,846,995, DE-A 37 11 299, US-A 4,904,408, US-A 4,846,994 and US-A 4,849,126) or modified celluloses such as e.g. B. Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
  • the detergents according to the invention can in particular contain soiling-releasing polymers, so-called soil-release polymers, which are generally composed of carboxylic acid units and, if appropriate, polymeric diol units and, for. B. contain ethylene terephthalate and polyoxyethylene terephthalate groups.
  • Other monomer units for example propylene glycol, polypropylene glycol, alkylene or alkenylene dicarboxylic acids, isophthalic acid, carboxy- or sulfo-substituted phthalic acid isomers can be contained in the soil release polymer.
  • End-capped derivatives ie polymers which have neither free hydroxyl groups nor free carboxyl groups but instead carry, for example, C 1 -C 4 -alkyl groups or are terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can be used.
  • polyesters known from European patent application EP 0 241 985 which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with C 1 -C 4 alkyl groups are end group-capped
  • the soil release polymers of ethylene terephthalate and polyethylene oxide terephthalate used in the agents of European patent application EP 0 253 567 with a molecular weight of 900 to 9,000, the polyethylene glycol units having molecular weights of 300 to 3,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95
  • the polyesters with polypropylene terephthalate and polyoxyethylene terephthalate units which are end-capped at least partly by C 1 -C 4 -alkyl or acyl radicals and which are known from European patent application EP 0 272 033 and which in the
  • Polymers made from ethylene terephthalate and polyethylene oxide terephthalate are also suitable which the polyethylene glycol units have molecular weights from 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10 and their use in detergents is described in German patent DE 28 57 292, and polymers with a molecular weight of 15,000 to 50,000 from ethylene terephthalate and po is polyethylene oxide terephthalate to polyethylene oxide terephthalate 2: 1 to 6: 1, which can be used in detergents according to German patent application DE 33 24 258.
  • the invention Textile detergent formulation usual color transfer inhibitors in the amounts usual for this (about 0.1 to 2 wt .-%) contain.
  • Color transfer inhibitors are, for example, homo- and Copolymers of vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone and 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000 and cross-linked, finely divided polymers based on these monomers used.
  • the use of such polymers mentioned here is known see. DE-B 22 32 353, DE-A 28 14 287, DE-A 28 14 329 and DE-A 43 16 023.
  • B Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds that have a diethanolamino group instead of the morpholino group, a methylamino group, an anilino group or a 1-methoxyethylamino group wear.
  • Brighteners of the type of substituted Diphenylstyryle be present, e.g. B.
  • Graying inhibitors have the task of that of the textile fiber to keep detached dirt suspended in the fleet.
  • water-soluble colloids mostly of an organic nature, for example Starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids the starch or the cellulose or salts of acidic Sulfuric acid esters of cellulose or starch.
  • water soluble, polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives other than those mentioned above can be used use, e.g. B. aldehyde starches.
  • Cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the composition, used.
  • the textile detergent formulation according to the invention alkaline additives, especially sodium carbonate and / or Sodium bicarbonate, in amounts of up to 40% by weight, especially 1 up to 25 wt .-%, and adjusting agents, in particular alkali metal sulfates such as Sodium sulfate, in amounts of up to 60% by weight, in particular 1 to 30% by weight.
  • water organic solvents include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol, and their mixtures and those derived from the compound classes mentioned Ether.
  • Such water-miscible solvents are in the agents according to the invention preferably in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkyl diamides. Mixtures of different foam inhibitors are also used with advantages, e.g. B. from silicone, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.
  • pH regulators are present in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17 % By weight.
  • the agents can also be used in detergents and cleaning agents Contain common ingredients.
  • these optional components include in particular enzyme stabilizers as well as dyes and fragrances, Corrosion inhibitors, clays, bactericides, phosphonates and abrasives contain.
  • the detergent or cleaning agent formulation according to the invention can Bleach activators, especially the quaternized glycine nitriles incorporated that they as pure components or as with suitable additives pre-assembled components in powder or Granules of detergent are included, or so that they are distributed as pure components or as pre-assembled with suitable additives Components as from the other detergent ingredients separated powder or granules are present.
  • Bleach activators especially the quaternized glycine nitriles incorporated that they as pure components or as with suitable additives pre-assembled components in powder or Granules of detergent are included, or so that they are distributed as pure components or as pre-assembled with suitable additives Components as from the other detergent ingredients separated powder or granules are present.
  • Incorporation of quaternized glycine nitriles as separated powder or granules, in particular as a product pre-assembled with suitable additives allows the gentle production of detergents with a special good stability of the bleach activator.
  • Uncompacted powder or granular detergents and cleaning agents usually have a low bulk density, usually from 200 to 600 g / l. You can also build a system based on Contain phosphate, be reduced in phosphate or be free of phosphate.
  • the washing and cleaning agent formulation according to the invention lies preferably in powder or granule form with a bulk density of 200 up to 1,100 g / l.
  • liquid formulations are also possible.
  • compositions according to the invention are not for use in Textile detergents limited, but can also be used for dishwashers, Stain removers (stain remover formulations), abrasives and descaling agents can be used.
  • This method can be used to determine the peracetic acid kinetics in raw materials and full products can be used.
  • TAED reacts to peracetic acid in the presence of hydrogen peroxide, which can be determined iodometrically. Thereby, through the titration on ice exploited the effect that only peracetic acid at low In contrast to temperatures, iodide is able to oxidize to iodine Hydrogen peroxide.
  • 1 g TAED are mixed with 4 g percarbonate in 1000 ml dist. Water (20 ° C) dissolved, analogously to 10 g of full product. From the time the samples were added to the water, the stopwatch was started and 10 ml was taken from the reacting mixture every 3 minutes. These 10 ml are pipetted onto approx. 50-100 g of ground ice. The sample / ice mixture is mixed with 10 ml of 8% KI solution and titrated rapidly with 0.1 Na thiosulfate solution to pale yellow. After adding a few drops of starch solution, titration is continued until it is colorless. The entire titration must run extremely quickly so that no distortion by hydrogen peroxide occurs. In addition, the temperature must be recorded when the sample is removed from the reaction vessel. After 10 pairs of values have been recorded, the values are shown graphically in a diagram.
  • Oil release polymer sodium sulfate, anti-foaming agent, brightener, phosphonate, Speckels, perfume ad 100
  • Each product is individually with 2/3 dosage without ballast at the prewashed later washing temperature.
  • Natural stains e.g. Spinach, cocoa, gravy, fries fat
  • the monitors are first cut and labeled.
  • the sampling takes place according to the school grade principle, for this purpose the 5 replicas of all test products are spread out on the table and then divided into groups. Afterwards there is a reasonable grade.
  • the average of 5 replicas is calculated and a duplicate Analysis of variance performed to provide statistical coverage receive.
  • washing test evaluation of various TAED bleach activator (BA) ratios at 30 ° C
  • a conventional heavy duty detergent (VWM) composition as described in Example 2 is used as the detergent.
  • Linitest uses four different fabrics, namely cotton, polyester, polyester / cotton and crude nettle.
  • the four types of fabric are each cut to a size of 10 cm x 15 cm, with the crude nettle being pre-washed in the washing machine with 170 ml of surfactant solution.
  • a lobule with the same full whiteness is now sought from each fabric, whereby this may fluctuate up or down by 1 whiteness.
  • the values are noted and then the initial Ry value is determined from each lobe.
  • a 10 cm x 15 cm WFK 10C soiling is added to each laundry for loading dirt.
  • Amount of wash liquor weight of the 5 tissues x 16 (liquor ratio)
  • the beakers of the Linite test are filled with the calculated amount of wash liquor, the tissues are introduced and the beakers are closed. After insertion, a certain heating output (here 30 ° C and 40 ° C) and the duration are set. After the set time, the lobules are taken out, rinsed and the whole process repeated accordingly.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP02028958.3A 2002-12-24 2002-12-24 Compositions de lavage et nettoyage optimisées pour un effet amélioré de blanchiment à basse température Expired - Lifetime EP1433839B2 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DK02028958.3T DK1433839T4 (da) 2002-12-24 2002-12-24 Optimeret vaske- og rengøringsmiddelsystem med henblik på forbedret blegevirkning ved lave temperaturer
DE50210897T DE50210897D1 (de) 2002-12-24 2002-12-24 Optimiertes Wasch- und Reinigungsmittelsystem für eine verbesserte Bleichwirkung bei niedrigeren Temperaturen
AT02028958T ATE373073T1 (de) 2002-12-24 2002-12-24 Optimiertes wasch- und reinigungsmittelsystem für eine verbesserte bleichwirkung bei niedrigeren temperaturen
ES02028958.3T ES2290242T5 (es) 2002-12-24 2002-12-24 Sistema de detergente y producto de limpieza optimizado para una acción blanqueante mejorada a bajas temperaturas
EP02028958.3A EP1433839B2 (fr) 2002-12-24 2002-12-24 Compositions de lavage et nettoyage optimisées pour un effet amélioré de blanchiment à basse température

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EP02028958.3A EP1433839B2 (fr) 2002-12-24 2002-12-24 Compositions de lavage et nettoyage optimisées pour un effet amélioré de blanchiment à basse température

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EP1433839B1 EP1433839B1 (fr) 2007-09-12
EP1433839B2 EP1433839B2 (fr) 2015-04-01

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008098921A1 (fr) * 2007-02-13 2008-08-21 Cht R. Beitlich Gmbh Solutions d'agents tensio-actifs stables au stockage pour blanchiment au peroxyde
WO2014139577A1 (fr) * 2013-03-14 2014-09-18 Ecolab Usa Inc. Composition de détergent pour textile pour lavage à basse température
GB202107968D0 (en) 2021-06-03 2021-07-21 Reckitt Benckiser Finish Bv Detergent gel composition comprising a fatty alcohol ethoxlate

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EP0790244A1 (fr) * 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
WO1998055579A1 (fr) * 1997-06-04 1998-12-10 The Procter & Gamble Company Systemes d'enzymes proteases mixtes pour eliminer les taches a base de proteines et compositions incorporant de tels systemes
DE19740669A1 (de) * 1997-09-16 1999-03-18 Clariant Gmbh Gecoatete Ammoniumnitril-Bleichaktivatorgranulate
DE19914353A1 (de) * 1999-03-31 2000-10-05 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit speziellen Bleichaktivatoren
DE19914812A1 (de) * 1999-03-31 2000-10-05 Henkel Kgaa Ein- oder mehrphasige Wasch- und Reinigungsmittelformkörper mit speziellen Bleichaktivatoren
US6174853B1 (en) * 1996-11-29 2001-01-16 Basf Aktiengesellschaft Textile detergent formulation on the basis of quaternized glycine nitriles, bleaching agents, nonionic and/or anionic tensides and calcium ion and/or magnesium ion sequestering compounds
DE10038180A1 (de) * 2000-08-04 2002-02-14 Reckitt Benckiser Nv Verwendung eines neuartigen Bleichaktivator-Compounds in Geschirrspülmittelzusammensetzungen
DE10049237A1 (de) * 2000-09-28 2002-04-11 Basf Ag Beschichtete, körnige N-Alkylammoniumacetonitril-Salze und deren Verwendung als Bleichaktivator
WO2002083829A1 (fr) * 2001-04-11 2002-10-24 Warwick International Group Limited Compositions activatrices de blanchiement melangees et procedes de blanchiement

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EP0106634B1 (fr) † 1982-10-08 1986-06-18 THE PROCTER & GAMBLE COMPANY Masses contenant des activateurs de blanchiment
GB9407532D0 (en) † 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
US5928929A (en) † 1995-02-10 1999-07-27 Novo Nordisk A/S Alkaline protease from bacillus sp.I612
DE10038845A1 (de) † 2000-08-04 2002-02-21 Henkel Kgaa Teilchenförmig konfektionierte Acetonitril-Derivate als Bleichaktivatoren in festen Waschmitteln

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Publication number Priority date Publication date Assignee Title
EP0790244A1 (fr) * 1996-02-15 1997-08-20 Hoechst Aktiengesellschaft Activateurs de blanchiment à de nitriles d'ammonium
US6174853B1 (en) * 1996-11-29 2001-01-16 Basf Aktiengesellschaft Textile detergent formulation on the basis of quaternized glycine nitriles, bleaching agents, nonionic and/or anionic tensides and calcium ion and/or magnesium ion sequestering compounds
WO1998055579A1 (fr) * 1997-06-04 1998-12-10 The Procter & Gamble Company Systemes d'enzymes proteases mixtes pour eliminer les taches a base de proteines et compositions incorporant de tels systemes
DE19740669A1 (de) * 1997-09-16 1999-03-18 Clariant Gmbh Gecoatete Ammoniumnitril-Bleichaktivatorgranulate
DE19914353A1 (de) * 1999-03-31 2000-10-05 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit speziellen Bleichaktivatoren
DE19914812A1 (de) * 1999-03-31 2000-10-05 Henkel Kgaa Ein- oder mehrphasige Wasch- und Reinigungsmittelformkörper mit speziellen Bleichaktivatoren
DE10038180A1 (de) * 2000-08-04 2002-02-14 Reckitt Benckiser Nv Verwendung eines neuartigen Bleichaktivator-Compounds in Geschirrspülmittelzusammensetzungen
DE10049237A1 (de) * 2000-09-28 2002-04-11 Basf Ag Beschichtete, körnige N-Alkylammoniumacetonitril-Salze und deren Verwendung als Bleichaktivator
WO2002083829A1 (fr) * 2001-04-11 2002-10-24 Warwick International Group Limited Compositions activatrices de blanchiement melangees et procedes de blanchiement

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008098921A1 (fr) * 2007-02-13 2008-08-21 Cht R. Beitlich Gmbh Solutions d'agents tensio-actifs stables au stockage pour blanchiment au peroxyde
WO2014139577A1 (fr) * 2013-03-14 2014-09-18 Ecolab Usa Inc. Composition de détergent pour textile pour lavage à basse température
GB202107968D0 (en) 2021-06-03 2021-07-21 Reckitt Benckiser Finish Bv Detergent gel composition comprising a fatty alcohol ethoxlate
WO2022253728A1 (fr) 2021-06-03 2022-12-08 Reckitt Benckiser Finish B.V. Composition de gel détergent comprenant un éthoxylate d'alcool gras
GB2607585A (en) 2021-06-03 2022-12-14 Reckitt Benckiser Finish Bv Detergent gel composition comprising a fatty alcohol ethoxylate

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DK1433839T4 (da) 2015-06-15
DE50210897D1 (de) 2007-10-25
EP1433839B1 (fr) 2007-09-12
ES2290242T3 (es) 2008-02-16
DK1433839T3 (da) 2008-01-21
ES2290242T5 (es) 2015-07-13
ATE373073T1 (de) 2007-09-15
EP1433839B2 (fr) 2015-04-01

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