EP0769045B1 - Waschmittel mit cellulase - Google Patents
Waschmittel mit cellulase Download PDFInfo
- Publication number
- EP0769045B1 EP0769045B1 EP95925775A EP95925775A EP0769045B1 EP 0769045 B1 EP0769045 B1 EP 0769045B1 EP 95925775 A EP95925775 A EP 95925775A EP 95925775 A EP95925775 A EP 95925775A EP 0769045 B1 EP0769045 B1 EP 0769045B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- acid
- detergent
- salt
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/221—Mono, di- or trisaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
Definitions
- SORMAN and the copolymers used according to the invention in a weight ratio of 10: 1 to 1: 3, in particular from 6: 1 to 1: 1.
- the advantage of the terpolymers over the conventional copolymers of Acrylic acid or the acrylate does not only consist in its biodegradability; rather, it has also been shown that when used contribute to even better graying inhibition with SORMAN.
- the terpolymers which are vinyl alcohol and / or Particularly contain vinyl acetate.
- the detergents according to the invention can be in solid, powdered form granular form. They preferably contain known surfactants, in particular anionic and nonionic, optionally also cationic, zwitterionic or amphoteric surfactants, builder substances, inorganic Salts such as carbonates, bicarbonates and silicates and optionally also neutral salts such as sodium sulfate, bleach if desired and other common ingredients of detergents.
- surfactants in particular anionic and nonionic, optionally also cationic, zwitterionic or amphoteric surfactants, builder substances, inorganic Salts such as carbonates, bicarbonates and silicates and optionally also neutral salts such as sodium sulfate, bleach if desired and other common ingredients of detergents.
- Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
- the alk (en) yl sulfates are the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length prefers.
- alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C.
- the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
- the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (E0) or C 12 - C 18 fatty alcohols with 2 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- preferred anionic surfactants are alkylbenzenesulfonates and / or Alk (en) yl sulfates, especially fatty alkyl sulfates.
- preferred Embodiment of the invention are 7 to 25 wt .-% Alkylbenzenesulfonates and / or alk (en) ylsulfate contained in the detergent.
- the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
- the anionic surfactants are preferably in Form of their sodium or potassium salts, especially in the form of the sodium salts in front.
- the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 E0 or 4 E0, C 9 -C 11 alcohol with 7 E0, C 13 -C 15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 E0.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- the alkyl glycosides can be present in the detergent in amounts of, for example, 1 to 5% by weight.
- alkoxylated fatty alcohols are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese Patent Application JP-A-58/217598 or which are preferably according to the method described in international patent application WO-A-90/13533.
- Nonionic surfactants are preferably used in the detergent in amounts of 0.5 to 25 wt .-% used. Quantities from 2 to 20 are advantageous % By weight and preferably 5 to 15% by weight of nonionic surfactants, in particular 50 to 100 wt .-%, based on the nonionic surfactants ethoxylated alcohols exist.
- the builders that can be used in detergents include phosphates, Zeolites and layered silicates.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
- zeolite NaX and mixtures of NaA and NaX are also suitable.
- the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
- Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline layered silicates are those in which M is sodium and x is 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
- Layered silicates are also suitable substitutes or partial substitutes for the zeolite natural and synthetic origin. Such layered silicates are for example from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405 known. Their usability is not up a special composition or structural formula is restricted. Prefers however, here are smectites, especially bentonites.
- small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the formulas above.
- the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca ++ .
- the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
- Useful sheet silicates are known, for example, from US-A-3,966,629, EP-A-0 026 529 and EP-A-0 028 432. Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
- Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their sodium salts, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures from these.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
- Suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble Salts such as those used in the international patent application WO-A-93/08251 are described or their production, for example, in of international patent application WO-A-93/16110.
- Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
- alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
- the sodium carbonate content of the agents is preferably up to 25% by weight, advantageously between 5 and 20% by weight.
- the sodium silicate content of the compositions is generally up to 15% by weight and preferably between 2 and 10% by weight.
- amorphous also means “X-ray amorphous” Understood. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as they do for crystalline ones Substances are typical, but at most one or more maxima scattered x-rays that are several units wide of the diffraction angle. However, it is very possible and can that the silicate particles even lead to particularly good builder properties washed out or even sharp in electron diffraction experiments Deliver diffraction maxima. This is to be interpreted as the products have microcrystalline regions of size 10 to a few hundred nm.
- silicates possibly also in combination with carbonates can be used as sole builder, then they can be used in the funds also in amounts of up to 40% by weight, preferably up to 30% by weight.
- Alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally having a further carboxyl and / or amino group Amino acids and / or their salts are replaced.
- a partial to complete exchange the alkali carbonates are made by glycine or glycinate.
- the other detergent ingredients include other common graying inhibitors, Foam inhibitors, bleaches and bleach activators, optical brighteners, enzymes, fabric softening substances, colors and fragrances, Pearlescent agents and neutral salts such as sulfates and chlorides in Form of their sodium or potassium salts.
- bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
- the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
- 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 bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
- the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
- the enzymes can be adsorbed on carrier substances and / or in coating substances embedded to protect them against premature decomposition.
- the amount of the enzymes, enzyme mixtures used in addition to the cellulase or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2 wt .-%.
- the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
- the agents can also contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
- boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
- graying inhibitors that can also be used water-soluble colloids mostly of an organic nature, for example Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose are preferred.
- Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures and polyvinylpyrrolidone. you will be for example in amounts of 0.1 to 5% by weight, based on the composition, used.
- the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, 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 which instead of the morpholino Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
- Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
- Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
- a particularly preferred dye is Tinolux (R) (commercial product from Ciba-Geigy).
- the bulk density of the preferred granular agents is generally 300 to 1200 g / l, in particular 500 to 1100 g / l.
- Suitable surface modifiers are from the state known in the art.
- Zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but especially mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.
- the agents according to the invention are particularly suitable for use at washing temperatures up to 60 ° C or below.
- Granular detergents of the following composition were produced and tested in a conventional manner.
- the components SORMAN, enzymes and copolymers were subsequently mixed into a spray drying product.
- test soiling consisted of dust-skin fat on one Blended fabric made of polyester and refined cotton (SH-PBV), dusty skin oil on cotton (SH-B), red lipstick on mixed fabric made of polyester and refined cotton (LS-PBV), milk soot on cotton (MR-B) and Milk cocoa on cotton (MK-B).
- Strips were made as white test fabric standardized cotton fabric (Krefeld laundry research institute; WFK), Bleaching nettle (BN), knitwear (cotton jersey; B) and terry cloth (FT) used.
- Washing conditions tap water of 23 ° d (equivalent to 230 mg CaO / l) with a calcium: magnesium ratio of 5: 1, amount of detergent used per detergent and machine 98 g, washing temperatures 40 or 60 ° C, liquor ratio (kg laundry added Liters of wash liquor) 1: 5.7, rinse four times with tap water, spin off and dry; Number of washes: 5 each for testing the primary washing performance, 10 each for testing graying inhibition; the reflectance was measured at 460 nm.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Description
Zusammensetzung | in Gew.-%: |
Natriumdodecylbenzolsulfonat | 9,0 |
C12-C18-Fettalkylsulfat | 3,0 |
C12-C18-Fettsäureseife | 2,0 |
C12-C18-Fettalkohol mit 5 E0 | 5,5 |
Talgfettalkohol mit 5 E0 | 1,0 |
Zeolith (wasserfreie Aktivsubstanz) | 30,0 |
Natriumcarbonat | 14,0 |
amorphes Natriumsilikat (Na2O : SiO2 1 : 2,0) | 2,0 |
CMC/MC | 1,0 |
Enzym-Granulat (Protease, Lipase) | 1,5 |
Cellulase (Cellozyme 0,7 T(R); Produkt der Firma Novo) | 1,0 |
Silikonöl | 0,5 |
Copolymere | (siehe Tabelle 1) |
SORMAN | (siehe Tabelle 1) |
Wasser | 10,0 |
Natriumsulfat (und andere Salze aus Lösungen) | Bilanz zu 100 |
Dabei bedeuten die Abkürzungen in Tabelle 1: SORMAN = Mischung aus Hexaacetylsorbitol und Hexaacetylmannitol im Gewichtsverhältnis 3 : 1 CP 5(R) = Copolymeres Salz der Acrylsäure und der Maleinsäure (Handelsprodukt der Firma BASF) Terpolymer = hergestellt aus 80 Gew.-% Acrylsäure und Maleinsäure im Gewichtsverhältnis 7 : 3 sowie aus 20 Gew.-% Vinylacetat gemäß der Offenbarung der älteren deutschen Patentanmeldung DE 43 00 772 mit anschließender vollständiger Neutralisation |
SORMAN | CP5(R) | Terpolymer | |
V1 | --- | 4,0 | --- |
V2 | --- | --- | 4,0 |
M1 | 5,0 | 4,0 | --- |
M2 | 5,0 | --- | 4,0 |
Primärwaschleistung bei 40 °C | ||
Remissionswerte in % für | ||
SH-PBV | LS-PBV | |
V1 | 67,1 | 55,0 |
M1 | 69,8 | 57,2 |
Vergrauungsinhibierung bei 40 °C (10 Wäschen) | |||||
Remissionswerte in % für | |||||
WFK | BN | B | FT | ||
Anfangswert | 86,4 | 85,1 | 87,4 | 88,4 | 86,8 |
V1 | 78,3 | 76,5 | 80,8 | 82,9 | 79,6 |
V2 | 79,8 | 79,0 | 80,2 | 82,8 | 80,5 |
M1 | 81,1 | 82,1 | 81,8 | 84,1 | 82,3 |
M2 | 81,7 | 82,1 | 83,0 | 83,9 | 82,7 |
Primärwaschleistung bei 60 °C | ||||
Remissionswerte in % für | ||||
SH-B | SH-PBV | MR-B | MK-B | |
V1 | 65,5 | --- | 76,0 | 73,8 |
V2 | --- | 68,8 | 81,3 | 74,0 |
M1 | 70,0 | --- | 82,8 | 75,7 |
M2 | --- | 71,1 | 82,6 | 76,0 |
Vergrauungsinhibierung bei 60 °C (10 Wäschen) | |||||
Remissionswerte in % für | |||||
WFK | BN | B | FT | ||
Anfangswert | 86,4 | 85,1 | 87,4 | 88,4 | 86,8 |
V1 | 61,3 | 64,5 | 65,3 | 66,8 | 64,5 |
V2 | 63,9 | 65,8 | 66,5 | 68,2 | 66,1 |
M1 | 66,0 | 70,7 | 69,8 | 72,2 | 69,7 |
M2 | 67,4 | 71,8 | 69,7 | 72,7 | 70,4 |
Claims (11)
- Waschmittel, enthaltend Cellulase, dadurch gekennzeichnet, daß es eine acetylierte Mischung aus Sorbitol und Mannitol enhält.
- Waschmittel nach Anspruch 1, dadurch gekennzeichnet, daß die acetylierte Mischung einen Acetylierungsgrad von 1 bis 6 und Sorbitol und Mannitol in einem Gewichtsverhältnis von 2,5 : 1 bis 4 : 1 aufweist.
- Waschmittel nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß es ein Copolymer enthält, wobei das Copolymer als eine Monomereinheit eine monoethylenisch ungesättigte C3-C8-Carbonsäure oder deren Salze aufweist.
- Waschmittel nach Anspruch 1 bis 3, dadurch gekennzeichnet, daß es ein Copolymer aus Monomereinheiten der Acrylsäure bzw. eines Salzes der Acrylsäure und der Maleinsäure bzw. eines Salzes der Maleinsäure und eine relative Molekülmasse von 5000 bis 200000 (auf Säure bezogen), vorzugsweise von 10000 bis 150000 und insbesondere von 50000 bis 120000 enthält.
- Waschmittel nach Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Copolymer ein Terpolymer ist, welches als Monomereinheit eine monoethylenisch ungesättigte C3-C8-Carbonsäure bzw. deren Salze, vorzugsweise Acrylsäure bzw. ein Salz der Acrylsäure, und eine monoethylenisch ungesättigte C4-C8-Dicarbonsäure bzw. deren Salz, vorzugsweise Maleinsäure bzw. ein Salz der Maleinsäure, sowie Vinylalkohol bzw. ein Vinylakohol-Derivat enthält.
- Waschmittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es Cellulase in Mengen von 0,2 bis 5 Gew.-% sowie eine acetylierte Mischung aus Sorbitol und Mannitol in Mengen von 1 bis 10 Gew.-% enthält.
- Waschmittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es eine acetylierte Mischung aus Sorbitol und Mannitol und ein Copolymer in einem Gewichtsverhältnis von 10 : 1 bis 1 : 3, insbesondere von 6 : 1 bis 1 : 1 enthält.
- Waschmittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es 2 bis 8 Gew.-% einer acetylierten Mischung aus Sorbitol und Mannitol und 0,5 bis 10 Gew.-% eines Copolymeren, insbesondere 1 bis 6 Gew.-% eines Copolymeren mit Bevorzugung eines Terpolymeren, welches als dritte Monomereinheit Vinylalkohol und/oder Vinylacetat enthält, aufweist.
- Waschmittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es frei von Peroxy-Bleichmittel ist.
- Verfahren zur Herstellung eines Waschmittels gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es durch Mischen, Sprühtrocknung, Granulieren und/oder Extrudieren hergestellt wird.
- Verwendung eines Waschmittels gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es bei Waschtemperaturen bis 60 °C oder darunter eingesetzt wird.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4424003 | 1994-07-07 | ||
DE4424003A DE4424003A1 (de) | 1994-07-07 | 1994-07-07 | Waschmittel mit Cellulase |
PCT/EP1995/002511 WO1996001886A1 (de) | 1994-07-07 | 1995-06-28 | Waschmittel mit cellulase |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0769045A1 EP0769045A1 (de) | 1997-04-23 |
EP0769045B1 true EP0769045B1 (de) | 1999-04-28 |
Family
ID=6522576
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95925775A Expired - Lifetime EP0769045B1 (de) | 1994-07-07 | 1995-06-28 | Waschmittel mit cellulase |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0769045B1 (de) |
AT (1) | ATE179456T1 (de) |
DE (2) | DE4424003A1 (de) |
ES (1) | ES2132689T3 (de) |
WO (1) | WO1996001886A1 (de) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NZ230842A (en) * | 1988-10-21 | 1992-05-26 | Colgate Palmolive Co | Nonionic heavy duty particulate detergent containing protease, amylase and cellulase |
JPH0356598A (ja) * | 1989-07-26 | 1991-03-12 | Kao Corp | 衣料用洗浄剤組成物 |
ATE155165T1 (de) * | 1991-07-31 | 1997-07-15 | Ausimont Spa | Verfahren zur erhöhung der bleichwirksamkeit eines inorganischen persalzes |
-
1994
- 1994-07-07 DE DE4424003A patent/DE4424003A1/de not_active Withdrawn
-
1995
- 1995-06-28 EP EP95925775A patent/EP0769045B1/de not_active Expired - Lifetime
- 1995-06-28 AT AT95925775T patent/ATE179456T1/de not_active IP Right Cessation
- 1995-06-28 WO PCT/EP1995/002511 patent/WO1996001886A1/de active IP Right Grant
- 1995-06-28 DE DE59505784T patent/DE59505784D1/de not_active Expired - Fee Related
- 1995-06-28 ES ES95925775T patent/ES2132689T3/es not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0769045A1 (de) | 1997-04-23 |
ATE179456T1 (de) | 1999-05-15 |
DE59505784D1 (de) | 1999-06-02 |
WO1996001886A1 (de) | 1996-01-25 |
DE4424003A1 (de) | 1996-01-11 |
ES2132689T3 (es) | 1999-08-16 |
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