EP1433839B2 - 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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EP1433839B2
EP1433839B2 EP02028958.3A EP02028958A EP1433839B2 EP 1433839 B2 EP1433839 B2 EP 1433839B2 EP 02028958 A EP02028958 A EP 02028958A EP 1433839 B2 EP1433839 B2 EP 1433839B2
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Prior art keywords
acid
detergent
taed
bleach activator
washing
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English (en)
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EP1433839B1 (fr
EP1433839A1 (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 AT02028958T priority Critical patent/ATE373073T1/de
Priority to EP02028958.3A priority patent/EP1433839B2/fr
Priority to ES02028958.3T priority patent/ES2290242T5/es
Priority to DK02028958.3T priority patent/DK1433839T4/da
Priority to DE50210897T priority patent/DE50210897D1/de
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Publication of EP1433839A1 publication Critical patent/EP1433839A1/fr
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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
    • C11D3/39—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 detergents or cleaners which have a bleaching effect at low temperatures.
  • Fabric detergent formulations as powders and as pressed molded articles usually contain a bleach system which consists mostly of active oxygen-supplying peroxo compounds, peracids or mixtures thereof and bleach activators.
  • the most commonly used bleach activator is tetraacetylethylenediamine ("TAED").
  • TAED tetraacetylethylenediamine
  • bleach activators are also known in the art. So describes z.
  • DE 100 38 844 A1 discloses a washing and cleaning agent containing a cationic bleach activator, this cationic bleach activator being an acetonitrile derivative with the anion of cumene sulfonic acid.
  • this bleach activator By adding this bleach activator, the bleach effect of aqueous peroxide liquors can be increased to such an extent in this application that substantially the same effect as with the peroxide liquor alone at 95 ° C. can be achieved even at temperatures below 60 ° C.
  • the application also describes the simultaneous use of the acetonitrile derivative with an enzyme to increase the cleaning performance of the washing and cleaning agent, especially against proteinaceous, starchy and / or colored stains, for use in aqueous washing and cleaning solutions, the contain a peroxygen compound.
  • Enzymes which are particularly described are enzymes which have a pH optimum, preferably in the alkaline range, up to about pH 10. A particular bleaching effect at low temperatures is not considered in this application.
  • EP 0 941 299 describes a laundry detergent formulation which contains quaternized glycine nitriles as bleach activators, bleaches, surfactants and a calcium- and / or magnesium sequestering compound having a builder or co-builder function in specific proportions to one another.
  • This detergent composition an improved bleaching effect is achieved at low washing temperatures (from 20 ° C to 60 ° C), especially when using this detergent formulation in hard water.
  • EP 0 778 832 is concerned with a process for preparing such quaternized glycine nitriles which can be used as a bleach activator in detergent compositions.
  • bleach activator namely an n-alkylammonium acetonitrile salt and its preparation are proposed in WO 00/58273.
  • German Offenlegungsschriften DE 100 38 832 and DE 100 38 845 describe various formulations of bleach activators of the quaternized aminoalkyl nitrile type or the acetonitrile derivatives for use in detergents.
  • WO 02/083829 relates to mixed bleach activator compositions.
  • the object of the present invention was to provide a detergent composition which develops good washing and bleaching performance at low temperatures (below 45 ° C).
  • a detergent composition containing at least one bleach activator and at least one TAED characterized in that the TAED is in a processing form which effects a peracetic acid release kinetics delayed to the bleach activator effect such that a peracetic acid concentration in the wash liquor of greater than 100 mg / l is reached only after at least 5 minutes, wherein as at least one bleach activator a quaternized glycine nitrile is used.
  • At least one bleach activator is a quaternized glycinonitrile.
  • all bleach activators may be used, show at temperatures below 45 ° C an activating for the bleaching action in washing liquors, these are, for example, compounds of the substance classes of polyacyliertem sugars or sugar derivatives with C 1 -C 10 acyl radicals, preferably acetyl , Propionyl, octanoyl, nonanoyl or benzoyl radicals, in particular acetyl radicals.
  • Mono- or disaccharides and their reduced or oxidized derivatives can be used as sugar or sugar derivatives.
  • 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.
  • O-acyl oxime esters such as e.g. O-acetylactone oxime, O-benzoylacetone oxime, bis (propylimino) carbonate or bis (cyclohexylimino) carbonate.
  • O-acyl oxime esters are described, for example, in EP-A-028 432 and EP-A-267 046.
  • N-acyl caprolactams such as N-acetyl caprolactam, N-benzoyl caprolactam, N-octanoyl caprolactam, N-octanoyl caprolactam, or carbonyl biscaprolactam, which patented uses at least one bleach activator, a quaternized glycine nitrile.
  • bleach activators in addition to the patented use of quaternized glycine nitrile as at least one bleach activator are 2-alkyl- or 2-aryl- (4H) -3,1-benzoxain-4-ones, as described, for example, in EP-B-332 294 and EP-B-502 013 are described.
  • 2-phenyl- (4H) -3,1-benzoxain-4-one and 2-methyl- (4H) -3,1-benzoxain-4-one can be used in addition to the patented use of quaternized glycine nitrile as at least one bleach activator ,
  • bleach activators from the classes of N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxybenzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose are used, wherein a quaternized glycinenitrile is used according to the patent as at least one bleach activator.
  • polyacylated alkylenediamines in particular
  • European Patent Application EP 0 464 880 discloses bleach-enhancing 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 having at least one 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 "and R"' are each a C 1 -C 24 alkyl or hydroxyalkyl group and the counteranion X - is an organic sulfonate, or a carboxylate.
  • At least one bleach activator is a quaternized glycine nitrile from the group consisting of N-methylmorpholinium acetonitrile methylsulfate, sulfate and hydrogen sulfate.
  • the activator can act as the sole bleach activator in the detergent composition are used, or in combination with one of the aforementioned bleach activators.
  • a combination of a quaternized glycine nitrile with TAED is used.
  • a quaternized glycinonitrile with TAED in a ratio of 4: 1 to 1: 4 is used.
  • Particularly preferred embodiments use a ratio of TAED to glycine nitrile of 4: 1, 3: 1 and 3: 2, the latter ratio being particularly suitable for textile detergents.
  • the improved washing performance is based on the fact that, at the beginning of the washing process, the bleach activator used, which is at least one quaternized glycine nitrile, is activated by too-rapid release of peracetic acid the TAED seems to be disturbed in its performance.
  • the bleach activator shows a significantly better effect, if at the beginning of the washing process, no very high peracetic acid concentration is present.
  • Properase the bleach activator has exerted its effect, it is advantageous for the washing result if the peracetic acid concentration increases in the course of the washing process.
  • Such a "delayed" occurrence of a high peracetic acid concentration improves in particular the bleaching action of the washing or cleaning agent according to the invention at low temperatures.
  • a TAED coated with a protective coating which dissolves only slowly in the wash liquor, and thus the TAED only takes effect with a delay, namely when the coating is removed.
  • the thickness of the coating influences the speed with which the TAED can come into effect. The thicker the coating, the longer it takes until the coating in the wash liquor is so far away that the TAED can unfold its effect.
  • a “delayed release” is meant that a concentration of more than 100 mg / l peracetic acid in the wash liquor occurs only after a few minutes, according to the patent after at least 5 min and preferably after at least 8 min. After this time, however, a rapid increase in the peracetic acid concentration in the wash liquor is desired.
  • TAED's with delayed or slow peracetic acid release kinetics are commercially available.
  • bleach activator which is at least one quaternized glycine nitrile
  • suitable bleaching agents which may be common, commonly known bleaches for detergent compositions, are added to the detergent composition.
  • suitable peroxygen compounds are in particular hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts to which alkali metal perborates such.
  • alkali metal perborates such as sodium perborate tetrahydrate and sodium perborate monohydrate
  • further alkali metal carbonate perhydrates such as sodium carbonate perhydrate ("sodium percarbonate") and persilicates and / or - persulfates such as caroate
  • the bleach system of the detergent formulation may contain inorganic or organic peracids, especially percarboxylic acids, e.g. B.
  • acids which can be used are peracetic acid, perbenzoic acid, linear or branched octane, nonane, decane or dodecane monoperacids, decane and dodecane diperacid, mono- and diperphthalic acids, isophthalic acids and terephthalic acids, phthalimidopercaproic acid, terephthaloyldiamidopercaproic acid and e-phthalimido peroxohexanoic acid ( PAP).
  • PAP phthalimidopercaproic acid
  • terephthaloyldiamidopercaproic acid e-phthalimido peroxohexanoic acid
  • 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 enveloped in a manner known in principle.
  • a particularly preferably used peracid is the peracid available under the trade name Eureco® (Ausimont, Italy).
  • Peroxygen compounds are present in amounts of preferably up to 50% by weight, more preferably from 5% to 30% and most preferably from 8% to 25% by weight.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • At least one bleach activator which is a quaternized glycine nitrile, and an effective peracid are present as raw materials side by side in the detergent formulation, however, their effect is offset in time by the sustained release of the peracid.
  • the peracid is in granular form.
  • This embodiment has the advantage that, regardless of the pH and washing temperature set in the wash liquor, a bleaching effect is achieved in each case entry. At low pH (pH 8.5 to 9), especially the effect of the peracid, which develops a bleaching effect without activation, comes to the fore. At higher pH (pH> 9) the bleach activator unfolds its full effect, so that here too an increased bleaching effect occurs.
  • various bleach activators namely those which exert their action at low temperatures (below 45 ° C) and those which exert their action at higher temperatures (from 40 ° C), may coexist as a mixture in the washing or cleaning composition. In this way, the temperature range in which the detergent can be used, be significantly widened.
  • the bleach catalysts used are usually quaternized imines or sulfonimines, as described, for example, in US Pat. No. 5,360,568, US Pat. No. 5,360,569 and EP-A-453,003, as well as manganese complexes, as described, for example, in WO-A 94/21777 are.
  • Other useful metal-containing bleach catalysts are described in EP-A-458,397, EP-A-458,398 and EP-A-549,272.
  • Bleach catalysts are generally used in amounts of up to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the detergent formulation.
  • Bleach stabilizers are additives which can adsorb, bind or complex interfering heavy metal traces during bleaching.
  • customary complexing agents such as ethylenediaminetetraacetate, nitrilotriacetic acid, methylglycinediacetic acid, .beta.-alaninediacetic acid, ethylenediamine-N, N'-disuccinate and phosphonates such as ethylenediamine tetramethylenephosphonate, diethylenetriaminepentamethylenephosphonate or Hydroxyethylidene-1,1-diphosphonic acid in the form of acids or as partially or completely neutralized alkali metal salts in amounts of up to 1 wt .-%, in particular 0.01 to 0.5 wt .-%, based on the detergent formulation used.
  • 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 enzymatically active protein per gram of the total composition.
  • the protein concentration can be determined by known methods, e.g. The bicinchonic acid method (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 As at least one washing-active enzyme, a protease is used which develops a substantial part of its activity at temperatures below 45 ° C.
  • An example of such a protease is the enzyme Properase.RTM ® 4000 E, which is marketed by Genencor International.
  • the other enzymes used may also be those which have an activity maximum at low temperatures. However, the enzymes used should develop a certain activity, at least at temperatures below 45 ° C, even though their maximum does not have to be there.
  • Suitable proteases include the enzymes obtainable from microorganisms, in particular bacteria or fungi, having a pH optimum in the alkaline range, for example those from international patent applications WO 92/07067, WO 91/02792, WO 88/03947 or WO 88/03946 or European patent applications EP 471 265, EP 416 967 or EP 394 352 known proteases.
  • Protease is preferably used in the composition according to the invention in amounts such that the finished composition contains 100 PE / g (protease units per gram, determined by the method described in Tenside 7, 125 (1970)), in particular 125 PE / g to 5,000 PE / g and more preferably 150 PE / g to 4500 PE / g.
  • Suitable proteases are commercially 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 proteases mentioned, the use of Properase® is particularly preferred.
  • amylases which can be used in the compositions according to the invention, which are preferably used in combination with at least one further enzyme, include the enzymes which can be obtained from bacteria or fungi and which have a pH optimum preferably in the alkaline range up to about pH 10.
  • Useful commercial products are, for example, amylase LT, Aquazym®. Duramyl®, Maxamyl®, Purastar®, Purafect® 0xAm or Termamyl®.
  • Amylase is preferably used in the composition according to the invention in amounts such that the finished product is from 0.01 KNU / g to 2 KNU / g ("kilo-novo units" per gram according to the standard method of the Company Novo, where 1 KNU is the amount of enzyme which builds 5.26 g of starch at pH 5.6 and 37 ° C, based on that of P. Bernfeld in SP Colowick and ND Kaplan, Methods in Enzymology, Volume 1, 1955, Page 149), in particular 0.015 KNU / g to 1.8 KNU / g and more preferably 0.03 KNU / g to 1.6 KNU / g.
  • the agent according to the invention contains an amylase, it is preferably selected from the genetically modified amylases. Genetically modified amylases are known, for example, from international patent applications WO 94/18314 or WO 95/21247.
  • the lipase optionally contained in the agent according to the invention is an enzyme which can be obtained from microorganisms, in particular bacteria or fungi.
  • microorganisms in particular bacteria or fungi.
  • 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 preferably used in the composition of the invention in amounts such that the finished composition has a lipolytic activity in the range of 10 LU / g to 10,000 LU / g ("Lipase Activity Units" per gram as determined by the enzymatic hydrolysis of tributyrin at 30 ° C and pH 7 according to the 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.
  • Commercially available lipases are, for example, Lipex®, Lipolase®, Lipolase Ultra®, Lipomax®, Lipoprime®, Lipozym® and Lumafast®,
  • the cellulase useful in the invention belongs to the enzymes obtainable from bacteria or fungi, which have a pH optimum preferably in the almost neutral to slightly alkaline pH range of 6 to 9.5.
  • Such Cellulases are known, for example, from German laid-open applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950, 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.
  • the composition according to the invention are preferably used in the composition according to the invention in amounts such that the finished composition has a cellulolytic activity of from 0.05 IU / g to 1.5 IU / g ("International Units" per gram, based on the enzymatic hydrolysis of Na-carboxymethylcellulose) pH 9.0 and 40 ° C, as described in Agric, Biol. Chem. 53, 1275 (1989) by S.Ito et al.), in particular 0.07 IU / g to 1.4 IU / g and particularly preferred 0.1 IU / G to 1.3 IU / g.
  • Suitable commercial products include, for example, Carezyme®, Celluzyme®, Ecostase®, and Novozym® from Novo Nordisk or KAC® from Kao.
  • the preferred cellulases include those from Melanocarpus sp. or Myriococcum sp. Available 20K cellulase known from international patent application WO 97/14804. It has as described there a molecular weight of about 20 kDa and has at 50 ° C in the pH range of 4 to 9 at least 80% of their maximum activity, while still maintaining almost 50% of the maximum activity at pH 10. It can, as also described there, be isolated from Melanocarpus albomyces and be produced in genetically engineered Trichoderma reseei transformants.
  • Suitable enzymes which can additionally be used in the compositions are those from the class of cutinases, pullulanases, hemicellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents.
  • the enzymes can, such as.
  • adsorbed on carriers and / or embedded in encapsulants to protect against premature inactivation are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight.
  • a mixture of two proteases is used in the washing or cleaning agent according to the invention, optionally together with other enzymes (amylase, lipase, cellulase).
  • Properase® in addition to another protease significantly improves the washing and cleaning properties of the washing and cleaning agent according to the invention, while at the same time less total amount of protease must be used, both in terms of the absolute amount used, as well as in terms of the international enzyme units used the enzymes. This additionally leads to a cost reduction in the production of the product produced.
  • Another advantage of reducing the total amount of protease is that a textile detergent produced in this way acts particularly gently on wool laundry.
  • Surfactants may be present in the detergent and cleaner composition as further customary detergent ingredients; nonionic and / or anionic surfactants or mixtures thereof are particularly preferred.
  • Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for. 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 first preparing a C 8 -C 22 -, preferably a C 10 -C 18 -alcohol, for.
  • a fatty alcohol alkoxylated and then sulfating the alkoxylation product.
  • 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 with propylene oxide alone and optionally 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 may contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in random distribution.
  • alkanesulfonates such as C 8 -C 24 -, preferably C 10 -C 18 -Alkansulfonate, and soaps such as the salts of C 8 -C 24 carboxylic acids.
  • anionic surfactants are C 9 -C 20 linear alkylbenzenesulfonates (LAS).
  • N-acylsarcosinates with aliphatic saturated or unsaturated C 8 -C 25 -acyl radicals, preferably C 10 -C 20 -acyl radicals, eg. B. N-Oleoylsarcosinate.
  • the anionic surfactants are added to the detergent formulation preferably in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium ions such. B. hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium ions.
  • linear alkylbenzenesulfonates and fatty alcohol sulfates are of particular interest.
  • Suitable nonionic surfactants are, for example, alkoxylated C 8 -C 22 -alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates.
  • the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide.
  • Suitable surfactants are all alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide added.
  • block polymers of ethylene oxide, propylene oxide and / or butylene oxide or adducts which contain the abovementioned alkylene oxides in random distribution.
  • Per mole of alcohol As a rule, 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • nonionic surfactants are alkylphenol ethoxylates having C 6 -C 14 alkyl chains and from 5 to 30 moles of ethylene oxide units.
  • alkyl polyglucosides of 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 units.
  • N-alkylglucamides of general structure II or III Wherein R 6 is C 6 -C 22 -alkyl, R 7 is H or C 1 -C 4 -alkyl and R 8 is a polyhydroxyalkyl radical having 5 to 12 C-atoms and at least 3 hydroxy groups.
  • R 6 is C 10 -C 18 alkyl
  • R 7 is methyl
  • R 8 is a C 5 -C 6 radical.
  • such compounds are obtained by acylation of reductively aminated sugars with acid chlorides of C 10 -C 18 carboxylic acids.
  • the textile detergent formulation according to the invention preferably contains ethoxylated nonionic surfactants with from 3 to 12 mol of ethylene oxide C 10 -C 16 -alcohols, in particular ethoxylated fatty alcohols and / or ethoxylated oxoalcohols.
  • Zeolites and silicates can be referred to in principle as inorganic ion exchangers.
  • Suitable zeolites are especially those of the type A, P, X, B, HS and MAP in their sodium form or in forms in which sodium is partially exchanged for other cations such as Li, K, Ca, Mg or ammonium.
  • Such zeolites are described, for example, in EP-A 0 038 591, EP-A 0 087 035, US Pat. No. 4,604,224, GB-A 2 013 259, EP-A 0 522 726, EP-A 0 384 070 and WO-A 94 / 24,251th
  • Suitable amorphous or crystalline silicates are above all amorphous disilicates and crystalline disilicates, such as the phyllosilicate SKS-6 (manufacturer: Hoechst).
  • the silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preferably, Na, Li and Mg silicates are used.
  • Particularly suitable alkali metal phosphate is trisodium polyphosphate, which may also be considered as an inorganic ion exchanger.
  • the group (i) comprises monoethylenically unsaturated C 3 -C 8 monocarboxylic acids such as.
  • acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid Preferably, from group (i), acrylic acid and methacrylic acid are used.
  • Group (ii) comprises monoethylenically unsaturated C 2 -C 22 -olefins, vinylalkyl ethers having C 1 -C 8 -alkyl groups, styrene, vinyl esters of C 1 -C 8 -carboxylic acids, (meth) acrylamide and vinylpyrrolidone.
  • C 2 -C 6 -olefins, vinyl alkyl ethers having C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate are preferably used from group (ii).
  • Group (iii) comprises (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) contain copolymerized vinyl esters, these can also be partially or completely hydrolyzed to vinyl alcohol structural units.
  • Suitable copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 and DE-A 43 13 909.
  • Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates are also contemplated.
  • suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid which are grafted in amounts of from 40 to 95% by weight, based on the component to be grafted.
  • Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).
  • a graft are degraded polysaccharides such.
  • polyethylene glycols ethylene oxide / propylene oxide or ethylene oxide / butylene oxide block copolymers, random ethylene oxide / propylene oxide or ethylene oxide / butylene oxide copolymers or alkoxylated mono- or polybasic C 1 -C 22 alcohols, cf. US-A 4,746,456.
  • Grafted degraded or degraded reduced starches and grafted polyethylene oxides are preferably used from this group, with from 20 to 80% by weight of monomers, based on the grafting component, being used in the graft polymerization.
  • Polyglyoxylic acids are described, for example, in EP-B 0 001 004, US Pat. No. 5,399,286, DE-A 41 06 355 and EP-A 0 656 914.
  • the end groups of the polyglyoxylic acids may have different structures.
  • Polyamidocarboxylic acids and modified polyamidocarboxylic acids are known, for example, from EP-A 0 454 126, EP-B 0 511 037, WO-A 94/01486 and EP-A 0 581 452.
  • 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 are preferably also used as aminopolycarboxylates. Particularly preferred are in phosphorus-containing Acids produced, with C 6 -C 22 mono- or dicarboxylic acids or with C 6 -C 22 mono- or diamines modified polyaspartic acids used.
  • Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds are, for. B. known from WO-A 93/22362 and WO-A 92/16493.
  • Such condensates containing carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.
  • zeolite A particularly preferred in 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 copolymers (especially those of molecular weight 10,000 to 100,000), polyaspartic acid, citric acid, nitrilotriacetic acid, methylglycinediacetic and mixtures used therefrom.
  • SKS-6 trisodium polyphosphate
  • acrylic acid / maleic copolymers especially those of molecular weight 10,000 to 100,000
  • polyaspartic acid especially those of molecular weight 10,000 to 100,000
  • citric acid especially those of molecular weight 10,000 to 100,000
  • nitrilotriacetic acid especially those of molecular weight 10,000 to 100,000
  • methylglycinediacetic especially those of molecular weight 10,000 to 100,000
  • mixtures of particular interest are those of 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 and zeolites, layered silicates and acrylic acid / maleic acid copolymers ,
  • the textile detergent formulation according to the invention may contain customary grayness inhibitors and / or soil-release polymers in the amounts customary for this purpose (about 0.1 to 2% by weight).
  • 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 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. Methylcellulose, hydroxypropylcellulose or carboxymethylcellulose.
  • the detergents according to the invention may comprise soil release polymers, so-called soil release polymers, which are generally composed of carboxylic acid units and optionally polymeric diol units and z.
  • soil release polymers which are generally composed of carboxylic acid units and optionally polymeric diol units and z.
  • ethylene terephthalate and polyoxyethylene terephthalate groups As 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 may be included in the soil release polymer.
  • end-capped derivatives ie polymers which have neither free hydroxyl groups nor free carboxyl groups, but carry, for example, C 1 -C 4 -alkyl groups or terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can be used.
  • polyesters disclosed in 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 also glycerol units C 1 -C 4 alkyl groups are end-capped, used in the agents of European Patent Application EP 0253567 soil release polymers of ethylene terephthalate and polyethylene oxide terephthalate having a molecular weight of 900 to 9,000, wherein the polyethylene glycol units have molecular weights from 300 to 3,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95, the polyesters disclosed in European Patent Application EP 0 272 033, at least partially terminated by C 1 -C 4 alkyl or acyl groups, with polypropylene terephthalate and polyoxyethylene terephthalate units disclosed in US Pat the European Patent Application EP 0 274 907
  • polymers of ethylene terephthalate and polyethylene oxide in in which the polyethylene glycol units have molecular weights of from 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is from 50:50 to 90:10 and their use in detergents is described in German Patent DE 28 57 292, and polymers having a molecular weight of from 15,000 to 50,000 of ethylene terephthalate and Polyethylene oxide terephthalate to polyethylene oxide terephthalate 2: 1 to 6: 1, which can be used according to the German patent application DE 33 24 258 in detergents.
  • the textile detergent formulation according to the invention may comprise customary color transfer inhibitors in the quantities customary for this purpose (about 0.1 to 2% by weight).
  • color transfer inhibitors for example, homopolymers and copolymers of vinylpyrrolidone, of vinylimidazole, of vinyl oxazolidone and of 4-vinylpyridine N-oxide having molecular weights of from 15,000 to 100,000 and crosslinked finely divided polymers based on these monomers are used.
  • the use of such polymers mentioned here is known, cf. DE-B 22 32 353, DE-A 28 14 287, DE-A 28 14 329 and DE-A 43 16 023.
  • the textile detergent formulation according to the invention may contain customary optical brighteners in the quantities customary for this purpose.
  • Suitable z. B salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 1-methoxyethylamino group wear.
  • brighteners of the type of substituted Diphenylstyryle be present, for.
  • Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids starch or 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 can be used, for. B. aldehyde levels.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.
  • the textile detergent formulation of the invention alkaline additives, especially sodium carbonate and / or sodium bicarbonate, in amounts of up to 40 wt .-%, in particular 1 to 25 wt .-%, and adjusting agents, in particular alkali metal sulfates such as sodium sulfate, in amounts of up to 60 wt .-%, in particular 1 to 30 wt .-%, contained.
  • organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the classes of compounds mentioned ether.
  • Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • 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 foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides.
  • mixtures of different foam inhibitors are used, for.
  • silicones 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. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • compositions of the invention system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or bases, in particular ammonium or alkali hydroxides.
  • environmentally acceptable acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or bases, in particular ammonium or alkali hydroxides.
  • pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • the agents may contain other ingredients customary in detergents and cleaners. These optional ingredients include in particular Enzyme stabilizers and colorants and fragrances, corrosion inhibitors, clays, bactericides, phosphonates and scouring agents.
  • the washing or cleaning agent formulation according to the invention may contain the bleach activators, which comprise at least one quaternized glycinonitrile incorporated in such a way that they are distributed as pure components or as prefabricated components with suitable additives in the powder or granules of the detergent, or in such a way that they pure components or as prefabricated with suitable additives components as separated from the other detergent ingredients powder or granules.
  • the incorporation of quaternized glycine nitriles as separated powder or granules, in particular as a product prefabricated with suitable additives allows the gentle production of detergents with a particularly good stability of the bleach activator.
  • Non-compacted powdered or granular detergents and cleaners usually have a low bulk density, usually from 200 to 600 g / l. They may also contain a phosphate-based builder system, phosphate-reduced or phosphate-free.
  • the detergent and cleaner formulation according to the invention is preferably in powder or granule form with a bulk density of 200 to 1100 g / l.
  • liquid formulations are also possible.
  • compositions of the invention are not limited to use in laundry detergents but can also be used for dishwashing detergents, stain removers (Stain salt formulations), scouring agents and descaling agents.
  • This method can be used to determine the peracetic acid kinetics in raw materials and whole products.
  • TAED reacts in the presence of hydrogen peroxide to peracetic acid, which can be determined iodometrically.
  • the titration on ice utilizes the effect that only peracetic acid is able to oxidize iodide to iodine at low temperatures, in contrast to hydrogen peroxide.
  • Detergent composition (Wt .-%) system Builder Sodium aluminum silicate 33 polycarboxylates 2 sodium 15 surfactant alkylbenzenesulfonate 2 Fatty alcohol sulfate 6 Nonionic 9 bleaching system sodium 15 Tetraacetylethylenediamine (TAED) 5 Cationic bleach activator (KB) 1 enzyme system protease ⁇ 1 Properase.RTM 0.2 amylase ⁇ 0.5 cellulase ⁇ 0.1 lipase ⁇ 0.5
  • Prewash Per test product Cotton (BW) 50 X 50 cm for 5 washes Polyester / cotton (PES / BW) 50 X 20 cm Polyester (PES) 50 X 20 cm 50 cm
  • Each product is individually prewashed at 2/3 dosage without ballast at the later washing temperature.
  • the Linitest uses four different fabrics: cotton, polyester, polyester / cotton and raw armchair.
  • the four fabric types are each cut to a size of 10 cm x 15 cm, wherein the raw bean is previously prewashed in the washing machine with 170 ml of surfactant solution.
  • each fabric For each series, each fabric is now searched for a lobe with the same whiteness, which may fluctuate up or down by 1 whiteness. The values are noted and then from each lobule the output Ry value is determined.
  • Amount of washing powder for 1 wash g of washing liquor ⁇ Dosing quantity for HB II in g 16 liquor ratio Amount of wash liquor weight of the 5 tissues x 16 (liquor ratio)
  • the cups of the linitol test are filled with the calculated amount of wash liquor, the tissues are introduced and the cups are closed. After inserting a certain heating power (here 30 ° C and 40 ° C) and the duration is set. After the set time, the lobules are taken out, rinsed and the whole process is repeated accordingly.
  • a certain heating power here 30 ° C and 40 ° C

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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)

Claims (6)

  1. Produit de lavage ou de nettoyage contenant au moins un activateur de blanchiment et au moins une TAED, caractérisé en ce que la TAED se présente sous une forme traitée, qui provoque une cinétique de libération d'acide peracétique retardée vis-à-vis de l'action de l'activateur de blanchiment à obtenir, dans la lessive de lavage, une concentration en acide peracétique supérieure à 100 mg/l, uniquement à l'issue d'une période d'au moins 5 mn, dans lequel on utilise comme au moins un activateur de blanchiment, un glycinonitrile quaternisé.
  2. Produit de lavage selon la revendication 1, contenant la TAED sous une forme revêtue et/ou condensée.
  3. Produit de lavage ou de nettoyage selon la revendication 1 ou 2, caractérisé en ce qu'il contient en plus une protéase, qui exerce une activité enzymatique maximale à des températures inférieures à 45 °C.
  4. Produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 3, contenant une combinaison d'un activateur de blanchiment efficace à basses températures (inférieures à 45 °C) avec un activateur de blanchiment efficace à des températures supérieures à 45 °C.
  5. Produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 4, dans lequel on utilise une combinaison de protéases efficaces à basses températures (inférieures à 45 °C) avec au moins une autre protéase.
  6. Utilisation d'un produit de nettoyage selon l'une quelconque des revendications 1 à 5, pour une application comme lessive textile, nettoyant de vaisselle, agent détachant (sel détachant), anti-calcaire ou abrasif, ou pour un usage dans l'un de ces produits.
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
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
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
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

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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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DE102007006908A1 (de) * 2007-02-13 2008-08-14 Cht R. Beitlich Gmbh Katalysierte Peroxidbleiche ("Katalysator-Bleiche")
EP2970823B1 (fr) * 2013-03-14 2021-06-30 Ecolab USA Inc. Composition de détergent pour textile pour lavage à basse température
GB2607585A (en) 2021-06-03 2022-12-14 Reckitt Benckiser Finish Bv Detergent gel composition comprising a fatty alcohol ethoxylate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106634A1 (fr) † 1982-10-08 1984-04-25 THE PROCTER & GAMBLE COMPANY Masses contenant des activateurs de blanchiment
WO1995028465A1 (fr) † 1994-04-13 1995-10-26 The Procter & Gamble Company Detergents contenant un adjuvant et une source de peroxyacide de blanchiment a liberation prolongee
US5928929A (en) † 1995-02-10 1999-07-27 Novo Nordisk A/S Alkaline protease from bacillus sp.I612
WO2002012425A1 (fr) † 2000-08-04 2002-02-14 Henkel Kommanditgesellschaft Auf Aktien Derives acetonitrile conçus sous forme particulaire servant d'activateurs de blanchiment dans des lessives solides

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DE19605526A1 (de) * 1996-02-15 1997-08-21 Hoechst Ag Ammoniumnitrile und deren Verwendung als Bleichaktivatoren
DE19649384A1 (de) * 1996-11-29 1998-06-04 Basf Ag Textilwaschmittel-Formulierung auf Basis von quaternierten Glycinnitrilen, Bleichmitteln, nichtionischen und/oder anionischen Tensiden und Calcium- und/oder Magnesiumionen sequestierenden Verbindungen
BR9810081A (pt) * 1997-06-04 2000-08-08 Procter & Gamble Sistemas de enzima protease mista para limpeza de sujeiras à base de proteìna e composições incorporando os mesmos
DE19740669A1 (de) * 1997-09-16 1999-03-18 Clariant Gmbh Gecoatete Ammoniumnitril-Bleichaktivatorgranulate
DE19914812A1 (de) * 1999-03-31 2000-10-05 Henkel Kgaa Ein- oder mehrphasige Wasch- und Reinigungsmittelformkörper mit speziellen Bleichaktivatoren
DE19914353A1 (de) * 1999-03-31 2000-10-05 Henkel Kgaa 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
GB0109137D0 (en) * 2001-04-11 2001-05-30 Warwick Internat Group Ltd Mixed bleach activator compositions and methods of bleaching

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EP0106634A1 (fr) † 1982-10-08 1984-04-25 THE PROCTER & GAMBLE COMPANY Masses contenant des activateurs de blanchiment
WO1995028465A1 (fr) † 1994-04-13 1995-10-26 The Procter & Gamble Company Detergents contenant un adjuvant et une source de peroxyacide de blanchiment a liberation prolongee
US5928929A (en) † 1995-02-10 1999-07-27 Novo Nordisk A/S Alkaline protease from bacillus sp.I612
WO2002012425A1 (fr) † 2000-08-04 2002-02-14 Henkel Kommanditgesellschaft Auf Aktien Derives acetonitrile conçus sous forme particulaire servant d'activateurs de blanchiment dans des lessives solides

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DK1433839T3 (da) 2008-01-21
EP1433839A1 (fr) 2004-06-30
ATE373073T1 (de) 2007-09-15
ES2290242T5 (es) 2015-07-13
DE50210897D1 (de) 2007-10-25
DK1433839T4 (da) 2015-06-15
ES2290242T3 (es) 2008-02-16

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