EP0937132A2 - Procede de fabrication d'agents de lavage et de nettoyage - Google Patents

Procede de fabrication d'agents de lavage et de nettoyage

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Publication number
EP0937132A2
EP0937132A2 EP97952752A EP97952752A EP0937132A2 EP 0937132 A2 EP0937132 A2 EP 0937132A2 EP 97952752 A EP97952752 A EP 97952752A EP 97952752 A EP97952752 A EP 97952752A EP 0937132 A2 EP0937132 A2 EP 0937132A2
Authority
EP
European Patent Office
Prior art keywords
granulation
weight
acid
granules
agents
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.)
Granted
Application number
EP97952752A
Other languages
German (de)
English (en)
Other versions
EP0937132B1 (fr
Inventor
Thomas Holderbaum
Thomas Merz
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
Ecolab Inc
Original Assignee
Henkel AG and Co KGaA
Henkel Ecolab GmbH and Co KG
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, Henkel Ecolab GmbH and Co KG filed Critical Henkel AG and Co KGaA
Publication of EP0937132A2 publication Critical patent/EP0937132A2/fr
Application granted granted Critical
Publication of EP0937132B1 publication Critical patent/EP0937132B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • C11D3/38672—Granulated or coated enzymes
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D3/3945—Organic per-compounds

Definitions

  • the present invention relates to a process for the production of particulate detergents and / or cleaning agents which contain both enzymes and bleaching agents by granulating the oxidizing agent component and mixing with the particulate compound enzyme component and optionally further particulate components.
  • the production of particulate detergents and cleaning agents can be carried out by mixing the individual particulate ingredients.
  • this can, for example due to different particle sizes and particle densities, lead to segregation of the ingredients and thus inconsistent performance of the agent.
  • Another difficulty arises from the fact that some ingredients of washing or cleaning agents are impaired in their effectiveness by the contact, which results from the mixing of the individual substances, with other ingredients of the same agent, or by contact with atmospheric oxygen or in the ambient air the water they contain will lose their effect.
  • enzymes normally contained in detergents and cleaning agents which are inactivated or destroyed by contact with bleaching agent components which are also common in such detergents and which, after short storage, can no longer contribute to the washing or cleaning performance of the detergents.
  • Conventional bleaching agents in the form of oxidizing agents based on oxygen are decomposed by atmospheric water or bleach activators are hydrolyzed by water and are then no longer available under the conditions of use.
  • Spray drying as a very common process for the production of particulate detergents and cleaning agents, is not suitable because of the thermal sensitivity of the bleaching agents or the enzymes to help solve these problems.
  • Granulation processes for the production of detergents or cleaning agents are known as an alternative to processes which have a spray drying step.
  • the conversion of previously spray-dried detergent ingredients into granules is also known. Reference can be made, for example, to the method known from European patent application EP 0 339 996, in which granules consisting of detergent components and obtained by spray drying are introduced into a high-speed mixer / granulator and pulverized there at high speed by the mixing tools and the knife.
  • the mixer then runs at a lower speed for the mixing tools and the knife, during which water is sprayed on as a granulating aid. After spraying, the mixer runs at a medium speed using mixing tools and knives to form granules from the solid and liquid components. After the granulation has ended, a finely divided amorphous sodium aluminum silicate is added to the mixer, the mixer being operated at a relatively slow speed of the mixing tools and the knife.
  • EP 0 351 937 describes a method for producing a detergent composition with increased bulk density. The granulation and compaction is carried out in a high-speed mixer. After completion of the granulation, it is possible to add 0.2 to 5% by weight of amorphous or 3 to 12% by weight of crystalline aluminum silicate at a low mixer speed in order to improve the flowability, with no further granulation occurring. Similar processes, but with different detergent compositions, are described in EP 0 340 013.
  • Another granulation process for producing granular detergents and cleaning agents is known from international patent application WO 93/23523.
  • two-stage granulation is carried out in two mixers / granulators connected in series.
  • the first, slow-running mixer 40% by weight to 100% by weight, based on the total amount of the solid and liquid constituents used, of the solid and liquid constituents are pregranulated.
  • the second, high-speed running Mixer the pre-granulate from the first process stage is mixed with the remaining solid and / or liquid constituents and transferred into the finished granulate.
  • German patent application DE 43 04 475 Another method for producing granulated detergents and cleaning agents is known from German patent application DE 43 04 475. This process is also carried out in two stages. In contrast to the processes already mentioned, in the first process stage there is no granulation or agglomeration, but only a mixing and loading of the added powder. In a second process step the starting materials from the first process step in a second mixer to be transferred, where the pulverfb 'shaped starting materials compacted by introduction of energy and the granules formed are rolled thereby compacting against each other. To stop the build-up roll granulation taking place here, a finely divided powder, for example zeolite powder such as zeolite NaA, is added to end the rolling process.
  • zeolite powder such as zeolite NaA
  • the invention was therefore based on the object of providing a particularly simple and economically working process for the production of particulate detergents and / or cleaning agents, as a result of which both bleaching agents and enzymes can be incorporated into the agents without both during the preparation and in the subsequent step Storage of the agents decreases the activity of the two ingredients mentioned unreasonably.
  • the invention relates to a process for the production of particulate detergents and / or cleaning agents which contain both enzyme and bleach, which is characterized in that the peroxygen-containing oxidizing agent component, optionally in the presence of inert solids, in a granulation mixer or compactor using Water and liquid nonionic surfactant are granulated or compacted as a granulation liquid and then mixed with the particulate enzyme component and optionally further particulate constituents.
  • customary mixers can be used in the method according to the invention for granulation purposes.
  • Suitable mixers are, for example, Eirich® mixers of the R and RV series (manufactured by Maschinenfabrik Gustav Eirich, Hardheim, Germany), the Fukae® FS-G mixers (manufactured by Fukae Powtech Kogyo Co, Japan), the Lödige® FM, KM and CB mixer (manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany) or the mixer of the Drais® series T or KT (manufactured by Drais Maschinene GmbH, Mannheim, Germany).
  • the usual residence time required for granulation in these mixers is in the range from 1 to about 10 minutes.
  • the aim of the granulation step in the process according to the invention is, in addition to the setting of a large number of physical variables, such as bulk density, solubility, water content, instant behavior, free-flowing properties, wettability, etc., the controlled grain build-up to a preliminary product which can be mixed with other components without the risk of subsequent segregation .
  • This can also be achieved by press agglomeration processes which can be carried out in a so-called compactor.
  • Suitable compactors are roller compactors, for example of the K, CS, G and MS series from Bepex® (Leingarten, Germany), which can also be used to produce small moldings such as briquettes or cylindrical pellets, tableting machines such as those from the company Fette® (Schwarzenbek, Germany) to the Manufacture of small tablets or flat matrix presses from Amandus Kahl® (Reinbek, Germany).
  • the granulation is preferably carried out at room temperature or at the temperature resulting from the energy input from the mixer or compactor.
  • the granules containing peroxygen-containing oxidizing agent produced in the granulation step of the process according to the invention preferably have an average diameter of up to 4 mm, in particular in the range from 0.2 mm to 1.6 mm and particularly preferably from 0.4 mm to 0.8 mm.
  • Any coarse grains, i.e. granules with a diameter above 2 mm, in particular with a diameter above 1.6 mm, are preferably sieved off after drying and can advantageously, after comminution, which can be carried out in a mill, for example, in the granulation step of the manufacturing process to be led back. It is also possible to recirculate fine-grain particles, i.e. granules with a diameter below 0.1 mm.
  • inorganic peroxygen compounds are used as the particulate oxidizing agents which are subjected to the granulation step according to the invention, alkali perborate tetrahydrate and alkali perborate monohydrates in addition to alkali percarbonate being particularly important.
  • suitable oxidizing agents are, for example, persulfates, peroxypyrophosphates, citrate perhydrates and HO 2 -supplying acid salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid.
  • Sodium percarbonate, sodium persulfate and / or sodium perborate monohydrate are preferably used.
  • inert solids ie solids which do not react either with the oxidizing agent or with the granulating liquid, can also be incorporated into the granulate.
  • alkali carbonates, bicarbonates, chlorides and sulfates these include, for example, alkalizing agents such as amorphous alkali silicates, and inorganic builder substances such as alkali phosphates, crystalline alkali silicates and finely divided alkali alumosilicates, in particular zeolites from Type A, X and / or P.
  • alkalizing agents such as amorphous alkali silicates
  • inorganic builder substances such as alkali phosphates, crystalline alkali silicates and finely divided alkali alumosilicates, in particular zeolites from Type A, X and / or P.
  • the preferred alkali metal is sodium in all cases.
  • Suitable zeolites normally have a calcium binding capacity of about 100 to 200 mg CaO / g, which can be determined according to the information in German patent DE 24 12 837. Their particle size is usually in the range from 1 ⁇ m to 10 ⁇ m.
  • Crystalline sheet silicates of the formula NaMSi x O 2 + x " yH 2 O, in which M represents hydrogen or sodium, x is a number of 1.9, are preferably used as crystalline silicates, which may be present alone or in a mixture with the alumosilicates mentioned to 4 and y is a number from 0 to 20. Preferred values for x are 2, 3 and 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP 164 514.
  • both ⁇ - and ⁇ -sodium disilicates are Na Si 0 5 yH 2 O is preferred, ⁇ -sodium disilicate being able to be obtained, for example, by the process described in international patent application WO 91/08171.
  • Usable crystalline silicates are available under the names SKS-6 (manufacturer Hoechst) and Nabion® 15 (manufacturer Rhone-Poulenc)
  • the proportion of such further solids in the granules containing the peroxidic oxidizing agent is preferably up to 80% by weight, ins particularly 10% by weight to 70% by weight and particularly preferably 20% by weight to 60% by weight, based on granules containing oxidizing agent.
  • the granulating liquid used to granulate the peroxidic oxidizing agent and optionally other solid constituents is essentially formed by water and nonionic surfactants, which are in liquid, that is pumpable and flowable, form at the process temperature, in particular at room temperature.
  • nonionic surfactants include addition products of 1 to 12 moles of ethylene oxide (EO) and / or propylene oxide (PO) to primary fatty alcohols with 10 to 22 carbon atoms and their mixtures such as coconut, tallow or oleyl alcohol, or in the 2-position methyl-branched primary alcohols (oxo alcohols).
  • C 12 -C 14 alcohols with 3 EO or 4 EO C 9 -C ⁇ alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, -C 2 -C ⁇ 8 alcohols with 3 EO, 5 EO or 7 EO and optionally 5 PO and mixtures of these, such as mixtures of -C 4 -C alcohol with 3 EO and C ⁇ 2 -C ⁇ 8 - alcohol with 5 EO, used.
  • 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 restricted homolog distribution (narrow range ethoxylates, NRE).
  • Alkyl glycosides of the general formula R' ⁇ (G) n can also be used, in which R 1 is a primary straight-chain or aliphatic radical which is branched in the 2-position methyl and has 8 to 22, preferably 12 to 18 C atoms and G is a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the average degree of oligomerization n which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10 and is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as can be prepared, for example, by the process described in international patent application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Other suitable surfactants are fatty acid polyhydroxyamides of the formula
  • the fatty acid polyhydroxyamides are substances which are usually obtained by reductive amination of a reducing sugar can be obtained with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the fatty acid polyhydroxyamides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • liquid nonionic surfactants can be used in a mixture with lower polyalkylene glycols which are derived from straight-chain or branched glycols having 2 to 6 carbon atoms.
  • Preferred lower polyalkylene glycols are polyethylene glycols or polypropylene glycols which have a relative molecular mass between 200 and 12,000, in particular between 200 and 4,000, for example up to 2,000.
  • the weight ratio of liquid nonionic surfactant to lower polyalkylene glycol in these mixtures is preferably 10: 1 to 1: 1.
  • the granulating liquid can optionally contain up to 90% by weight of water. In one embodiment of the invention, however, it preferably consists of at least 95% by weight of nonionic surfactant and is preferably used in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 6% by weight , based on the resulting granules.
  • the granulating liquid can be heated to temperatures of up to 40 ° C before it enters the granulation mixer or compactor. However, it is preferably used at room temperature. If the granulation liquid has several ingredients, these can be used together or separately, that is to say individually.
  • the granulate thus produced which contains the oxidizing agent containing peroxygen, is mixed according to the invention with at least one enzyme-shaped enzyme.
  • enzyme-shaped enzyme Those from the class of proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof are particularly suitable, the use of protease, amylase, lipase and / or cellulase being particularly preferred.
  • the proportion of enzyme-containing particles in the washing or cleaning agent produced according to the invention is preferably 0.2% by weight to 5% by weight and in particular 0.3% by weight to 2% by weight.
  • Protease used together with particulate amylase e.g. Termamyl® 60T or Maxamyl® CXT.
  • the enzymes can be adsorbed onto carrier substances in a customary manner and / or embedded in coating substances, as is known, for example, from European patent EP 168 526 or international patent applications WO 93/07260, WO 93/07263 or WO 95/02031.
  • An enzyme-containing extrudate which can be obtained using the method known from European Patent EP 0 564 476, is preferably used.
  • Proteases that can be used are, for example, from international patent applications WO 91/02792, WO 92/21760, WO 93/05134, WO 93/07276, WO 93/18140, WO 93/24623, WO 94/02618, WO 94/23053, WO 94 / 25579, WO 94/25583, WO 95/02044, WO 95/05477, WO 95/07350, WO 95/10592, WO 95/10615, WO 95/20039, WO 95/20663, WO 95/23211, WO 95 / 27049, WO 95/30010, WO 95/30011, WO 95/30743 and WO 95/34627.
  • Enzymes stabilized against oxidative damage are preferably used, for example the proteases or amylases known under the trade names Durazym® or Purafect® OxP or Duramyl® or Purafect® OxAm.
  • a detergent or cleaning agent prepared according to the invention can contain the particulate-formulated enzymes further, by simply incorporating them, with particulate constituents which can have the usual ingredients in such agents.
  • these include, for example, further surfactants, in particular anionic surfactants, additional builder substances, bleach activators, graying inhibitors, soil-release active substances, optical brighteners, foam regulators and colorants and fragrances.
  • the grain size distribution of such admixing components For reasons of homogeneity, it should not be fundamentally different from the particle size distributions of the granules which contain the peroxygen-containing oxidizing agent and the enzyme in the form of particles.
  • the bleaching agent component contained in agents produced by the process according to the invention can also contain bleach activators in addition to the peroxygen-containing oxidizing agent.
  • the oxidizing power of the above-mentioned peroxygen-based oxidizing agents can be improved by using bleach activators which form peroxocarboxylic acids under perhydrolysis conditions.
  • bleach activators especially from the substance classes of the N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles , Diketopiperazines, sulfurylamides and cyanurates, also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, sodium isononanoyl-oxybenzenesulfonate and triacetin (glycerol triacetate), and acylated sugar derivatives, as has become known, pentose acetate, pentose acetate.
  • multiply acylated alkylenediamines in particular tetraacetyl
  • a bleach activator is preferably used which forms peracetic acid under the washing conditions, with tetraacetylethylenediamine being particularly preferred.
  • bleach activators By adding bleach activators, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that even at temperatures around 60 ° C essentially the same effects occur as with the peroxide liquor alone at 95 ° C.
  • Bleach activators are preferably contained in washing or cleaning agents produced according to the invention in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight.
  • transition metal salts and complexes as for example in European patent applications EP 0 392 592, EP 0 443 651, EP 0 458 397, EP 0 544 490, EP 0 549 271, EP 0 630 964 or EP 0 693 550 proposed, as so-called bleaching catalysts, in addition to or instead of the conventional bleaching activators, to increase the bleaching performance.
  • bleaching catalysts in addition to or instead of the conventional bleaching activators, to increase the bleaching performance.
  • Particularly suitable are those known from German patent applications DE 195 29 905, DE 195 36 082, DE 196 05 688, DE 196 20 41 1 and DE 196 20 267 as bleach-activating catalysts Transition metal complexes.
  • Bleach-activating transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are present in the inventive agents in amounts of preferably up to 1% by weight, in particular 0.0025% by weight to Contain 0.25% by weight.
  • the bleach activators and / or bleach catalysts are preferably not incorporated into the granules containing the peroxidic oxidizing agent, but instead are prepared in particulate form by known methods, as disclosed, for example, in European patent EP 0 037 026, and mixed with the other particulate constituents of the composition.
  • Preferred anionic surfactants of the sulfonate type are Cg-Co-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and also disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C 2 -C 8 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the anionic surfactants which can be used also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Cg to C 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
  • esters of ⁇ -sulfofatty acids are also suitable, for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable anionic surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 1 -C 2 o-oxoal - alcohols, and those of secondary alcohols of this chain length.
  • the Sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C9-C ⁇ alcohols with an average of 3.5 moles of ethylene oxide are suitable.
  • Fatty alcohol mixtures which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol, are also preferred.
  • Mixtures are preferred in which the proportion of the alkyl radicals is 30 to 60% by weight on C 18 , 15 to 40% by weight on C 12 , 15 to 25% by weight on C 6 , 5 up to 15% by weight on C 14 and less than 1% by weight on C 10 .
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 18 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Anionic surfactants are preferably used in amounts of from 0.5% by weight to 5% by weight, in particular from 1% by weight to 3% by weight, in agents prepared according to the invention. They are preferred in the form of separate surfactant-containing granular components which are conventionally prepared by spray drying aqueous slurries, by spray neutralization in accordance with German patent application DE 44 25 968 or by granulation and, if appropriate, simultaneous drying in a fluidized bed in accordance with the teaching of international patent applications WO 93/04162 or WO 94/18303 can be obtained, incorporated into agents produced according to the invention.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, succinic acid, glutaric acid, adipic acid, tartaric acid and nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these.
  • Polymeric polycarboxylates come into consideration as further organic builder substances. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • the content of the (co) polymeric polycarboxylates is preferably 0.5 to 8% by weight.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • 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, for example degraded starch or aldehyde starches.
  • carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and also polyvinylpyrrolidone, if appropriate in mixtures with the cellulose derivatives, are preferably used in amounts of up to 5% by weight, in particular from 0.5% by weight to 2% by weight.
  • the usual foam regulators which can be used in compositions produced according to the invention include, for example, polysiloxane / silica mixtures, the fine-particle silica contained therein preferably being silanated.
  • the polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof.
  • Further defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, the melting point of which is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, for example sodium behenate, and alkali metal salts of phosphoric acid mono- and / or dialkyl esters in which the alkyl chains each have 12 to 22 carbon atoms.
  • the foam regulator active ingredients can be made up in granular particle form by known methods, for example as described in German patent application DE 43 23 411 or in international patent applications WO 91/12306 or WO 95/02699.
  • the proportion of foam regulator granules in the agent produced according to the invention can preferably be 0.5% by weight to 2% by weight.
  • a suitable selection of the nonionic surfactants can reduce the tendency to foam, so that the use of defoaming agents can be dispensed with entirely.
  • optical brighteners the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or similar compounds, instead of the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Substituted 4,4'-distyryl-di-phenyl brighteners may also be present, e.g.
  • the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl Mixtures of the aforementioned brighteners can also be used.
  • the optical brighteners are preferably dissolved in the nonionic surfactants used as the granulating liquid.
  • the ingredients enzyme and peroxidic oxidizing agent which are normally endangered in terms of their stability, are present in a stable manner next to one another even when stored for a prolonged period.
  • the agents prepared according to Example 1 were stored for 4 weeks at 40 ° C and 80% relative humidity. The agents then had the active oxygen contents and protease activities given in Table 1 below, each expressed as a percentage of the respective value directly after production.

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EP97952752A 1996-10-26 1997-10-17 Procede de fabrication d'agents de lavage et de nettoyage Expired - Lifetime EP0937132B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19644591A DE19644591A1 (de) 1996-10-26 1996-10-26 Verfahren zur Herstellung enzym- und bleichmittelhaltiger Wasch- und Reinigungsmittel
DE19644591 1996-10-26
PCT/EP1997/005751 WO1998018899A2 (fr) 1996-10-26 1997-10-17 Procede de fabrication d'agents de lavage et de nettoyage

Publications (2)

Publication Number Publication Date
EP0937132A2 true EP0937132A2 (fr) 1999-08-25
EP0937132B1 EP0937132B1 (fr) 2004-09-15

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ID=7810111

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97952752A Expired - Lifetime EP0937132B1 (fr) 1996-10-26 1997-10-17 Procede de fabrication d'agents de lavage et de nettoyage

Country Status (4)

Country Link
EP (1) EP0937132B1 (fr)
AT (1) ATE276349T1 (fr)
DE (2) DE19644591A1 (fr)
WO (1) WO1998018899A2 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19824688A1 (de) * 1998-06-03 1999-12-09 Henkel Kgaa Amylase und Percarbonat enthaltende Wasch- und Reinigungsmittel
EP1760141A1 (fr) * 2005-09-06 2007-03-07 SOLVAY (Société Anonyme) Peroxycarboxylique acide granulé enveloppé, procédé de préparation et utilisation dans la blanchissage, le blanchiment et la désinfection

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3519570A (en) * 1966-04-25 1970-07-07 Procter & Gamble Enzyme - containing detergent compositions and a process for conglutination of enzymes and detergent compositions
US3664961A (en) * 1970-03-31 1972-05-23 Procter & Gamble Enzyme detergent composition containing coagglomerated perborate bleaching agent
US3789001A (en) * 1972-03-09 1974-01-29 Colgate Palmolive Co Detergent containing enzyme and coarse perborate particles
DE3682443D1 (de) * 1985-06-28 1991-12-19 Procter & Gamble Granulierte zusammensetzung enthaltend ein trockenes bleichmittel und ein stabiles enzym.
JP2925794B2 (ja) * 1991-08-20 1999-07-28 花王株式会社 漂白洗浄剤組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9818899A2 *

Also Published As

Publication number Publication date
DE59711919D1 (de) 2004-10-21
EP0937132B1 (fr) 2004-09-15
WO1998018899A3 (fr) 1998-07-23
DE19644591A1 (de) 1998-04-30
ATE276349T1 (de) 2004-10-15
WO1998018899A2 (fr) 1998-05-07

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