EP0696313A1 - Poudre detergente comportant un adjuvant silicatique, une combinaison tensioactive particuliere et une lipase - Google Patents

Poudre detergente comportant un adjuvant silicatique, une combinaison tensioactive particuliere et une lipase

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Publication number
EP0696313A1
EP0696313A1 EP94913611A EP94913611A EP0696313A1 EP 0696313 A1 EP0696313 A1 EP 0696313A1 EP 94913611 A EP94913611 A EP 94913611A EP 94913611 A EP94913611 A EP 94913611A EP 0696313 A1 EP0696313 A1 EP 0696313A1
Authority
EP
European Patent Office
Prior art keywords
weight
alkali
nonionic surfactant
ethoxylated nonionic
surfactants
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.)
Withdrawn
Application number
EP94913611A
Other languages
German (de)
English (en)
Inventor
Jörg Poethkow
Horst Upadek
Beatrix Kottwitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0696313A1 publication Critical patent/EP0696313A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • Powder detergent with a silicate builder special combination of surfactants and lipase
  • the invention relates to a detergent which contains alkali silicate and, if appropriate, zeolite as a builder, and surfactants, lipase and, if appropriate, a peroxy bleach and other customary constituents.
  • zeolite in particular zeolite NaA
  • mixtures of zeolite with alkali silicates and alkali carbonates and polymeric polycarboxylates are used as phosphate substitutes in washing and cleaning agents.
  • complexing agents such as the salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and phosphoric acids.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • phosphoric acids phosphoric acids
  • European patent application EP 0 291 869 describes phosphate-free builders (builder systems) made from zeolite, aminoalkane polyphosphonate and / or polymeric polycarboxylate and l-hydroxyethane-l, l-di-phosphonate (HEDP), certain weight ratios of the last three components relating to a synergism the prevention of the formation of fiber incrustations. Crystalline, layered sodium silicates have also been described as substitutes or partial substitutes for phosphates and zeolites.
  • European patent application EP 0164 514 discloses a phosphate-free builder combination which mainly contains crystalline phyllosilicates of the formula Na Si x ⁇ 2 ⁇ + ryH2 ⁇ , 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.
  • These layered silicates can be used as water softeners both separately and in detergents and cleaning agents together with other builders such as phosphates, zeolite, other silicates, phosphonates and polycarboxylates.
  • European patent applications EP 337 217 and EP 337 219 disclose combinations of builders for detergents which contain crystalline layered silicates and optionally phosphates and polycarboxylates such as citrates, glyconates, NTA and / or inodiacetates but no zeolite.
  • European patent application EP 405 122 specifies a builder combination for textile detergents, which consists of a mixture of zeolite and crystalline sodium phyllosilicate in a ratio of 4: 1 to 1: 4.
  • Enzymes are also known as further constituents of detergents, in particular proteases and amylases, but also lipases.
  • a detergent which contains anion (preferably ABS, ether sulfate, olefin sulfonate) and / or nonionic surfactant (preferably nonylphenyl, alkyl polyethoxylate) and lipase, preferably in an amount of 10 to 100000 LU / g, from Pseudomonas plantarii and possibly contains builder.
  • European patent application EP 0341 999 describes a surfactant composition which consists of at least 30% by weight of non-ionic surfactants selected from alkoxylate adducts with fatty alcohols, fatty acids, fatty acid esters, fatty acid amides and fatty amines with at least 10 carbon atoms in the molecule, where the average content of the alkylene oxide groups per molecule is less than 5, and also contains anionic surfactants, so that the total content of surfactant on average is 1 to 30% by weight and also contains lipase in an amount of 0.005 to 100 LU / mg based on the total agent.
  • non-ionic surfactants selected from alkoxylate adducts with fatty alcohols, fatty acids, fatty acid esters, fatty acid amides and fatty amines with at least 10 carbon atoms in the molecule, where the average content of the alkylene oxide groups per molecule is less than 5, and also contains anionic surfactants, so that the total content of surfactant on
  • German patent application DE 41 06880 describes a detergent composition which contains a finely divided, hydrated zeolite, a solid alkali silicate and peroxy bleach, anionic, nonionic and zwitterionic surfactants, with the proviso that this detergent is free from water-soluble organic complexing agents the group of substituted phosphonates and is free of polymeric carboxylates and free of alkali metal carboxylates.
  • a fatty alcohol with 5 ethylene oxide units is primarily used as the nonionic surfactant.
  • the detergent above with a builder system based on Zeo ⁇ lith and sodium silicate are indeed ecologically because of their phosphate freedom particularly 'advantageous detergent, but they require special production technologies because of its excipients, bility to their Handhab ⁇ and in particular to ensure the powder properties, without impairing performance at the same time.
  • the simple replacement of the lower ethoxylated alcohols with higher ethoxylated alcohols can lead to a deterioration in the washing power.
  • the object of the invention was to further develop the field of phosphate-free builders in combination with other ingredients for use in textile detergents, with the aim of achieving good handling, that is to say good powder properties, of the detergent while maintaining the performance of the detergent.
  • detergents which contain certain alkali silicates or combinations of alkali alumosilicate and alkali silicate as a builder and a mixture of higher and lower ethoxylated surfactants together with lipase meet these requirements.
  • the invention relates to a particulate detergent which contains alkali silicate with a molar ratio of alkali oxide to SiO 2 under 1, nonionic surfactants and lipase, optionally finely divided, hydrated alkali alumosilicate, anionic surfactants and peroxy bleach and other additives, and is characterized in that that it contains 1% by weight to 10% by weight of low ethoxylated, nonionic surfactants and 1% by weight to 10% by weight of higher ethoxylated, nonionic surfactants.
  • low ethoxylation means an average degree of ethoxylation of 1 to 7, in particular 1 to 6, and higher ethoxylation means an average degree of ethoxylation of 8 to 20.
  • the alkali silicates contained in the agents according to the invention as builders preferably have a molar ratio of alkali oxide to SiO 2 below 0.95 ' , in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio a2 ⁇ : Si ⁇ 2 of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil ( R ). Those with a molar ratio a2 ⁇ : Si ⁇ 2 of 1: 1.9 to 1: 2.8 can be produced according to the method of European patent application EP 0425427.
  • Crystalline sheet silicates of the general formula Na2Si x ⁇ 2 ⁇ + i * yH2 ⁇ , in which x, the so-called modulus, a number from 1.9 to 4 and y one, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates Number is from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0164514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • both ⁇ - and fr-sodium disilicate (Na2S ⁇ ' 2 ⁇ 5 * H2 ⁇ ) are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
  • ⁇ '-sodium silicates with a modulus between 1.9 and 3.2 can according to the Japanese patent applications JP 04/238809 or JP 04/260610 can be produced.
  • the content of alkali silicates in the agents according to the invention is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali alumosilicate, in particular zeolite, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, based in each case on water-free active substances, is then preferably 4: 1 to 10: 1. In agents which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • the optionally used finely crystalline and bound water-containing alkali alumosilicate is preferably synthetic zeolite of the A type in detergent quality.
  • Mixtures of zeolite NaA and NaX are also suitable, the proportion of zeolite NaX in such mixtures advantageously being less than 30%. They have practically no particles larger than 30 ⁇ m and preferably consist at least 80% of particles smaller than 10 ⁇ m.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (measurement method: Eisenhofer diffraction; mean volume distribution), preferably between 1.5 ⁇ m and 4.5 ⁇ m, in particular between 2.0 ⁇ m and 4.0 ⁇ m.
  • the calcium binding capacity which is determined according to the information in German patent DE 24 12837, is in the range from 100 to 200 mg CaO / g.
  • the zeolite generally has a water content of 17% by weight to 25% by weight, in particular 18% by weight to 22% by weight.
  • the detergent according to the invention can contain up to 10% by weight, preferably 1% by weight to 5% by weight, of alkali carbonate, in particular sodium carbonate.
  • Polymeric carboxylates or polymeric carboxylic acids may also be present as additional builders. These polymeric carboxylates or carboxylic acids can preferably be present in the detergent according to the invention in an amount of up to 8% by weight, in particular up to 2% by weight.
  • Polymeric carboxylates or polymeric carboxylic acids with a relative molecular weight of at least 350 in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, are suitable, such as polyacrylates, polyhydroxyacrylates, polymethacrylates, polymaleates and in particular copolymers of Acrylic acid with maleic acid or maleic anhydride, preferably those made from 50 to 70% acrylic acid and 50 to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • the proportion of acid is at least 50% by weight.
  • Terpolymers which contain two carboxylic acids and / or their salts as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as a third monomer can also be used as polymeric carboxylates or carboxylic acids.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cg-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C / j-Cß-dicarboxylic acid, preferably a Ctt-Cß-dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives are preferred which are an ester of short-chain carboxylic acids, for example C 1 -C 10 -carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60 to 95% by weight, in particular 70 to 90% by weight of (meth) acrylic acid or (meth) acrylic acid, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 to 40% by weight .-%, preferably 10 to 30 wt .-% vinyl alcohol and / or vinyl acetate.
  • Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular are particularly preferred 2.1 and 2.5: 1. Both the amounts and the weight ratios are based on the acids.
  • the second acidic monomer or its salt can also be a derivative of an alkylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably from benzene or benzene -Derivatives derives, is substituted.
  • Preferred terpolymers contain 40 to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 to 30% by weight, preferably 15 to 25 % By weight of methyl sulfonic acid or methyl sulfonate and as a third monomer 15 to 40% by weight, preferably 20 to 40% by weight of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • the terpolymers used can be produced by any of the known and customary processes.
  • Terpolymers which are neutralized either completely or at least partially, in particular to more than 50%, based on the carboxyl groups present, are also preferably used.
  • a completely neutralized terpolymer is particularly preferred, ie it consists of the salts of the monomeric acids, in particular the sodium or potassium salts of the monomeric acids, and vinyl alcohol or a carbohydrate.
  • the terpolymers generally have a relative molecular mass between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They are mostly used in the form of aqueous solutions, preferably in the form of 30 to 50% by weight aqueous solutions.
  • Particularly preferred terpolymers are produced by a process which is described in German patent applications P 4221 381.9 and P 4300772.4.
  • the detergents according to the invention can contain customary water-soluble complexing agents from the group of the phosphonates.
  • Salts of polyphosphonic acids such as neutral sodium salts of, for example, 1-hydroxyethane-l, 1-diphosphonate and diethylenetriapentamethylenephosphonate are used.
  • the phosphonates can be used in amounts of up to 1.5% by weight, but these additives are preferably dispensed with, so that the detergents according to the invention have a calculated phosphorus content of 0%.
  • the detergents and cleaning agents contain known compounds from the group of nonionic surfactants as further constituents, and anionic and zwitterionic surfactants can also be present.
  • the surfactants are generally present in the detergents according to the invention with a total content of from 5% by weight to 40% by weight, preferably from 5% by weight to 30% by weight and in particular from 8% by weight to 25% by weight .-% in front.
  • the detergent according to the invention contains a combination of low-ethoxylated with higher-ethoxylated non-ionic surfactants, in particular alcohol ethoxylates, as nonionic surfactants.
  • the non-ionic surfactants can be present in an amount of 2% by weight to 25% by weight, preferably 2% by weight to 15% by weight.
  • the ethoxylated alcohols used as nonionic surfactants are derived from primary alcohols with preferably 9 to 18 carbon atoms.
  • the lower ethoxylated alcohols have an average of 1 to 7, in particular 1 to 6, moles and the higher ethoxylated alcohols have an average of 8 to 20 moles of ethylene oxide per mole of alcohol.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • the alcohol radical can be linear or ethyl-branched in the 2-position, or contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, e.g. B. from coconut, tallow or oleyl alcohol.
  • the preferred low-ethoxylated alcohols include, for example, fatty alcohols with 12 to 18 carbon atoms with an average of 3 to 5 EO units.
  • the preferred higher ethoxylated alcohols include, for example, fatty alcohols with 16 to 18 carbon atoms with an average of 12 to 16 EO units, e.g. ethoxylated tallow alcohol.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE), as can be produced, for example, by the process of German patent application DE 3843 713 using certain hydrotalcite catalysts.
  • the detergents according to the invention contain 1% by weight to 10% by weight, preferably 1% by weight to 5% by weight of low-ethoxylated nonionic surfactants and 1% by weight to 10% by weight, preferably 1% by weight. - up to 5% by weight of higher ethoxylated nonionic surfactants.
  • the lower ethoxylated alcohols and the higher ethoxylated alcohols are preferably in a weight ratio of 10: 1 to 1:10, in particular 5: 1 to 1: 5, particularly preferably 2: 1 to 1: 1.
  • nonionic surfactants that can be used in addition to the combination of the above-mentioned low-ethoxylated and higher-ethoxylated nonionic surfactants are alkoxylated fatty acid methyl testers, as described, for example, in the Japanese patent application. avoidance JP 58/217598 or which are preferably produced by the method described in international patent application WO 90/13533.
  • the agents according to the invention can also contain, as further nonionic surfactants, alkyl glycosides of the general formula R0 (G) p, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms means and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms means and G stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization p which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; p is preferably 1.2 to 1.4.
  • Alkyl glycosides can be present in the detergents according to the invention in an amount of 0 to 5% by weight,
  • anionic surfactants are sulfates and, if appropriate, sulfonates and soaps made from preferably natural fatty acids or fatty acid mixtures. Overall, anionic surfactants can be present in the agents according to the invention in an amount of up to 25% by weight, preferably up to 15% by weight and in particular from 3% by weight to 12% by weight.
  • Suitable sulfate-type surfactants are sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • alk (en) yl sulfates the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o-C2 ⁇ -O ⁇ oa alcohols, and those secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Ci6-Ci8-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 Ci6-Ci8-alk (en) yl sulfate in combination with lower-melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and which have relatively low 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 Ci2-Ci4-fatty alkyl sulfates or Ci2-Ci6-fatty alkyl sulfates with Ci5-Ci8-fatty alkyl sulfates.
  • fatty alkyl sulfates preferably mixtures of Ci2-Ci4-fatty alkyl sulfates or Ci2-Ci6-fatty alkyl sulfates with Ci5-Ci8-fatty alkyl sulfates.
  • unsaturated alkenyl sulfates with an alkenyl chain length of preferably C16-C22 are used.
  • Mixtures of saturated, predominantly C15 sulfonated fatty alcohols and unsaturated, sulfonated fatty alcohols predominantly consisting of Cj ⁇ are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the type HD-0z, enol ( R ) (commercial product of the applicant ). Weight ratios of alkyl sulfates to alkenyl sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.
  • the agents according to the invention can contain up to 12% by weight alk (en) yl sulfates, preferably 5 to 8% by weight.
  • the sulfuric acid monoesters of the straight-chain or branched C7 ⁇ C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci2-Ci8 -Fatty alcohols with 2 to 4 EO are suitable. Because of their high foaming power, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • surfactants of the sulfonate type preference is given to using C9-C13-alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from Ci2-Ci8-monoolefins with a terminal or internal double bond through sulfonate. form with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • These surfactants can be present in a content of up to 10% by weight, preferably up to 5% by weight.
  • surfactants of the sulfonate type can also be dispensed with without significantly impairing the washing action.
  • Soaps are particularly suitable as further anionic surfactants, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, being suitable are.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-Ci8 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • a detergent according to the invention preferably contains soap in amounts of 0.1% by weight to 1.5% by weight.
  • the lipase contained in the agent according to the invention is an enzyme which can be obtained from microorganisms, in particular bacteria or fungi. Such are known, for example, from European patent applications EP 204 208, EP 214 761, EP 258 068, EP 407 225 or international patent application WO 87/859.
  • Useful commercially available lipases are, for example, Lipolase ( R ) and Lipozym ( R ).
  • Lipase is used in the agent according to the invention preferably in amounts such that the finished agent 100 LU / g to 900 LU / g ("lipase activity units" per gram, determined via the enzymatic hydrolysis of tributyrin at 30 ° C. and pH 7 according to the method mentioned in EP 258 068), in particular 150 LU / g to 800 LU / g and particularly preferably 200 LU / g to 450 LU / g.
  • the enzymes are embedded in the agents according to the invention in a form adsorbed on carrier substances, in Hü11 substances or in the form of conventional granules with inorganic and / or organic carrier materials, as for example in the German patent specification DE 16 17 232, the German patent application DT 2032766 or DE 4041752 or the European patent applications EP 168 526, EP 170360, EP 270608 or EP 304 331.
  • the enzymes according to the invention may contain further enzymes, in particular those from the class of proteases, amylases, cellulases or mixtures thereof.
  • Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Strepto yces griseus are particularly suitable.
  • These enzymes can also be used on carriers adsorbed and / or embedded in coating substances to protect them against premature decomposition.
  • the enzymes can be contained separately in up to four separate particles or in the form of multi-enzyme granules, as described, for example, in international patent applications WO 90/09440 or WO 90/09428 and the prior art cited therein.
  • the detergents according to the invention preferably contain peroxy bleaching agents and in particular peroxy bleaching agents in combination with bleach activators.
  • peroxy bleaching agents include sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance.
  • Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-delivering peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the detergents preferably contain 5% by weight to 25% by weight and in particular 10% by weight to 20% by weight of bleach.
  • bleach activators can be incorporated into the preparations that form organic peracids with H2O2.
  • these are N- or 0-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, in particular tetraacetylglycoluril, N-acylated hydatoines, hydrazides, triazoles, triazines, urazoles, diketopiperazines, sulfuryl amides and also carbonic acid uridamides and cyanuric acid amides and carbonic acid urides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl
  • the bleach activator may have been coated with coating substances in a known manner or, if appropriate using granulating aids, may have been granulated and, if desired, may contain further additives, for example dye.
  • Such granules preferably contain more than 90% by weight, in particular from 94% by weight to 99% by weight, of bleach activator.
  • a bleach activator is preferably used which forms peracetic acid under the washing conditions.
  • TAED tetraacetylethylenediamine
  • carboxymethylcellulose with average grain sizes of 0.01 up to 0.8 mm
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,5,5-triazine
  • the content of bleach activators in the detergents containing bleaching agents is in the usual range, preferably between 1% by weight and 10% by weight and in particular between 3% by weight and 8% by weight.
  • detergent components the proportion of which, depending on the composition of the detergent, is normally 0.1 to 5% by weight, include foam inhibitors, optical brighteners, fabric softening agents, colorants and fragrances. It may also be neutral salts in 'contain an amount up to 20 wt .-%, but their proportion is preferably ⁇ 10 wt .-%.
  • the agent according to the invention can contain graying inhibitors, preferably in an amount of 0.1% by weight to 5% by weight, based on the agent.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the graying of the fibers.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch or aldehyde starches.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8-24 ⁇ f : fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their Mixtures with microfine, optionally silanized silica as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also advantageously used, for example those made from silicones and 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 bistearylethylene diamides are particularly preferred.
  • powdery or granular detergents contain 1% by weight to 5% by weight of low-ethoxylated nonionic surfactants, 1% by weight to 5% by weight of higher ethoxylated nonionic surfactants, 8% by weight to 10% by weight.
  • % other surfactants 30% by weight to 40% by weight of a finely divided, hydrated zeolite with an average particle size of 2.0 ⁇ m to 3.8 ⁇ m, 2% by weight to 10% by weight of amorphous sodium silicate with one molar Na2 ⁇ : Si ⁇ 2 ratio of 2.0 to 2.8 or a mixture of the amorphous sodium silicate mentioned with crystalline layered silicate, preferably ⁇ -sodium disilicate or ⁇ '-sodium disilicate, 18% by weight to 30% by weight peroxy bleach, preferably perborate and / or percarbonate, and 1% by weight to 3% by weight of a bleach activator, preferably TAED or DADHT, and 100 to 900 LU / g lipase.
  • a bleach activator preferably TAED or DADHT
  • the detergents according to the invention can be prepared in a manner known per se, for example by mixing, granulating and / or by spray drying. It is possible to incorporate the inorganic builders alkali alumosilicate and alkali silicate, if both are to be used, individually into the agents in a manner known per se and in any order.
  • the pourable powdery or granular compositions preferably consist of a dry homogeneous mixture of at least two powder components, the first of which is in the form of spray-dried granules. It can be obtained by spray drying a slurry which is carried out in a conventional manner and which contains at least the anionic surfactants and, if appropriate, the aluminosilicate or inorganic filler salts in an aqueous solution Slurry or suspension and optionally contains nonionic surfactants. If required, the bleaching agent present is not spray-dried together with the constituents of this first powder component, as is customary because of its thermal sensitivity, but is only mixed in subsequently.
  • the alkali silicate is preferably not spray-dried, but mixed in in granular form or adsorbed onto a carrier, which can consist, for example, of sulfate and / or carbonate.
  • a carrier which can consist, for example, of sulfate and / or carbonate.
  • zeolite / alkali silicate incompatibility it is preferably not spray-dried with a zeolite-containing slurry under spray drying conditions.
  • the agents according to the invention can be produced in a very simple manner by mixing the powder component or powder components mentioned with the lipase or enzyme particles in a conventional mixer, in particular a drum, roller, belt or free-fall mixer, with optional other powdery components and if desired, liquid or liquefied constituents, which include in particular nonionic surfactants, but also colorants and fragrances, can be admixed by spraying.
  • a conventional mixer in particular a drum, roller, belt or free-fall mixer
  • liquid or liquefied constituents which include in particular nonionic surfactants, but also colorants and fragrances
  • the detergent according to the invention is also intended to contain further ingredients, it is preferred to convert these components, insofar as they are thermally resilient, into a powder product in a known manner by spray drying an aqueous slurry and to mix this with the aforementioned powder components and enzymatic active ingredients and optionally other thermally sensitive constituents, to which bleaching agents in particular, for example alkali perborates or alkali percarbonate, are to be counted.
  • bleaching agents in particular, for example alkali perborates or alkali percarbonate
  • the incorporation of the other constituents by admixing a granulate or extrudate containing them with the other constituents is also possible and is particularly preferred for the production of detergents with a relatively high bulk density of preferably 650 g / 1 to 900 g / 1.
  • Granular detergents of the following composition were produced and tested.
  • the components mentioned in the first to sixth place and zeolite NaA and sodium sulfate were mixed to form an aqueous spray batch and spray-dried in a test tower.
  • the perborate, the bleach activator and the enzyme granules were subsequently mixed into the spray product.
  • Exemplary recipes of the detergents used are listed in Table 1, recipe A of a composition according to DE 41 06 880, recipe B of a comparative composition which cannot be assigned to the prior art or to the invention, and C to G in each case one of the inventions appropriate composition.
  • Zeolite NaA anhydrous
  • 38.0 38.0 38.0 38.0 0 0 0 average particle size 3.3 ⁇ m
  • Sokalan CP ⁇ ( R ) acrylic acid-maleic acid copolymer sodium salt, commercial product from BASF
  • Ciss-Cis fatty alcohol 4 ethoxylated Ciss-Cis fatty alcohol with an average of 14 EO units.
  • test fabrics were provided with bleachable stains (fat / pigment stains) that could be broken down by enzymes.
  • bleachable stains fat / pigment stains
  • the use of a powder detergent according to the invention gave comparable or better results in terms of whiteness than the powder detergent of the prior art (measurement using a Zeiss reflectometer at 465 nm, masking out the brightener effect).
  • Agents C, E, F and G according to the invention performed under these test conditions at least as well as agent D.

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

Abstract

L'invention concerne un détergent qui contient du silicate alcalin dans un rapport molaire de l'oxyde alcalin au SiO2 inférieur à 1, entre 1 et 10 % en poids de tensioactif non ionique faiblement éthoxylé et dont l'indice moyen d'éthoxylation est compris entre 1 et 7, et entre 1 et 10 % en poids de tensioactif non ionique fortement éthoxylé et dont l'indice moyen d'éthoxylation est compris entre 8 et 20. Le détergent contient en outre une lipase et éventullement de l'aluminosilicate alcalin hydraté, à fines particules, des tensioactifs anioniques et des décolorants peroxydiques, ainsi que d'autres additifs. Ce détergent est d'une utilisation aisée et conserve toute son efficacité de lavage.
EP94913611A 1993-04-28 1994-04-19 Poudre detergente comportant un adjuvant silicatique, une combinaison tensioactive particuliere et une lipase Withdrawn EP0696313A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19934313949 DE4313949A1 (de) 1993-04-28 1993-04-28 Pulverwaschmittel mit ökologisch unbedenklichem Buildersystem, spezieller Tensidkombination und Lipase
DE4313949 1993-04-28
PCT/EP1994/001210 WO1994025558A1 (fr) 1993-04-28 1994-04-19 Poudre detergente comportant un adjuvant silicatique, une combinaison tensioactive particuliere et une lipase

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EP0696313A1 true EP0696313A1 (fr) 1996-02-14

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EP (1) EP0696313A1 (fr)
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Publication number Priority date Publication date Assignee Title
CA2254068A1 (fr) * 1996-05-15 1997-11-20 Procter & Gamble European Technical Center Compositions detergentes comprenant une enzyme lipolytique specifique et une zeolite map
GB0030671D0 (en) 2000-12-15 2001-01-31 Unilever Plc Detergent compositions
GB0030669D0 (en) 2000-12-15 2001-01-31 Unilever Plc Detergent compositions
GB0124308D0 (en) * 2001-10-10 2001-11-28 Unilever Plc Detergent compositions
GB0124307D0 (en) 2001-10-10 2001-11-28 Unilever Plc Detergent compositions
DE102012200673A1 (de) * 2012-01-18 2013-07-18 Henkel Ag & Co. Kgaa Wasch-, Reinigungs- oder Vorbehandlungsmittel mit erhöhter Reinigungskraft

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GB8811045D0 (en) * 1988-05-10 1988-06-15 Unilever Plc Enzymatic detergent composition
GB8826110D0 (en) * 1988-11-08 1988-12-14 Unilever Plc Enzyme-containing detergent compositions
ES2083560T3 (es) * 1991-04-12 1996-04-16 Procter & Gamble Composicion detergente compacta que contiene polivinilpirrolidona.
CA2140287C (fr) * 1992-07-15 1999-09-21 Abdennaceur Fredj Compositions inhibitrices de transfert hydrotypique de colorants, contenant des agents de blanchiment

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Title
See references of WO9425558A1 *

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WO1994025558A1 (fr) 1994-11-10

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