EP0777722A1 - Produit liquide de lavage ou de nettoyage a pouvoir blanchissant - Google Patents

Produit liquide de lavage ou de nettoyage a pouvoir blanchissant

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Publication number
EP0777722A1
EP0777722A1 EP95930440A EP95930440A EP0777722A1 EP 0777722 A1 EP0777722 A1 EP 0777722A1 EP 95930440 A EP95930440 A EP 95930440A EP 95930440 A EP95930440 A EP 95930440A EP 0777722 A1 EP0777722 A1 EP 0777722A1
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EP
European Patent Office
Prior art keywords
weight
agent
composition according
surfactants
enzymes
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
EP95930440A
Other languages
German (de)
English (en)
Other versions
EP0777722B1 (fr
Inventor
Hans-Josef Beaujean
Christian Block
Rainer Hofmann
Dieter Legel
Rudolf Lind
Josef Penninger
Bernd Richter
Reiner Schackmann
Karl Schwadtke
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
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Henkel AG and Co KGaA
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Priority claimed from DE19944428958 external-priority patent/DE4428958A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0777722A1 publication Critical patent/EP0777722A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles

Definitions

  • the invention relates to a non-aqueous agent for washing or cleaning with bleach, which in addition to the bleaching agent contains nonionic and anionic surfactants and builders, and a process for the preparation of this agent.
  • aqueous agents for washing and cleaning contain anionic and nonionic surfactants.
  • bleach systems it has proven very difficult to incorporate bleach systems into these agents.
  • the use of bleaching agent systems is therefore often dispensed with in these agents, which leads to a reduction in the washing performance in the case of bleachable soiling.
  • Some liquid detergents available on the market contain very special bleach systems, which, however, either have very low oxidation potential or are unstable and disintegrate even with short storage times, which does not improve the washing activity of bleachable soiling.
  • non-aqueous liquid detergents made from liquid nonionic surfactants are known, which can contain 20 to 70% by weight of builder substances and 1 to 20% by weight of bleaching agent in suspended form.
  • anionic surfactants such as alkylbenzenesulfonates, olefin sulfonates, alkyl sulfates or soap, optical brighteners, dyes, fragrances or enzymes can be added to these agents.
  • EP-B-0 460 810 describes a non-aqueous, liquid detergent composition for dishwashers which comprises a non-aqueous, organic carrier liquid and at least one component selected from organic cleaning agent, cleaning agent builder, foam inhibitor and mixtures thereof and a component selected from a non-abrasive amount of 0.5 to 10% of small, essentially water-insoluble particles of silicon dioxide, aluminum oxide or titanium oxide or mixtures thereof as anti -Filming agent ent ⁇ contains.
  • the agent described may further contain 3 to 15% by weight of bleach.
  • WO 94/01524 describes an essentially non-aqueous liquid detergent which, in addition to nonionic surfactant, contains up to 60% by weight of builder substance and between 5 and 35% by weight of bleach.
  • the liquid detergent composition described also contains a polymer compound which reduces the viscosity of the dispersion of the solid builders and bleaches in the nonionic surfactant in order to obtain a flowable and pourable composition.
  • German patent application 36 26 572 describes a liquid detergent which contains builder substance, in particular polyacetal carboxylate, a gel-preventing agent and a sediment-preventing agent, dispersed in a liquid nonionic surfactant.
  • Liquid detergents containing bleach that can be stored can only be obtained if the bleach is in the form of a stable dispersion.
  • the commercially available liquid detergents known from the publications mentioned above have the disadvantage that further auxiliaries are necessary to obtain a stable dispersion. Since the dispersion present in the commercially available liquid detergents is only a limited, stable dispersion, it is not possible to incorporate bleaching agents and enzymes next to one another in these products, since the bleaching agent destroys the enzymes.
  • liquid detergents tend to gel, especially if they are stored cold or used at low washing temperatures.
  • the gel formation has the consequence that the liquid detergents are poorly soluble, which on the one hand deteriorates the washing power and on the other hand the agent cannot be completely rinsed out of the dispenser or a conventional dosing aid while the washing machine is in operation. Redispersion of the gel in the detergent composition is very difficult.
  • gel formation leads to a significant increase in viscosity, which in turn impairs the meterability of the liquid detergent.
  • the viscosity of the liquid detergent should not be too low in order to prevent sedimentation of the solid components as far as possible.
  • liquid detergents containing bleach for washing or cleaning is a further difficulty.
  • Stable dispersions of the solid particles in the liquid phase are generally obtained when the solid particles have a small particle size and narrow particle size distribution. Because of the different production processes, the particle size of the builder particles and of the bleaching agent particles is very different, which leads to a very broad particle size distribution. Solid particles with large diameters in particular lead to unstable dispersions.
  • the present invention has for its object to provide a stable, bleaching liquid detergent for washing and cleaning, which contains the solid bleaching agents in the form of a stable dispersion, even if they have been stored for a long period of time, without the activity of to impair substances contained therein and which may also contain components sensitive to bleach.
  • Another object of the invention is to provide a method for producing these agents.
  • the present invention accordingly relates to a non-aqueous liquid detergent for washing or cleaning which contains more than 20 to less than 78% by weight of nonionic surfactants, 0.1 to 25% by weight of anionic surfactants, 1 to less than Contains 20 wt .-% water-soluble builder substances and more than 20 to 35 wt .-% bleach.
  • the agent according to the invention is a special combination of washing or cleaning ingredients contains, whereby a flowable and storage-stable liquid agent for washing and cleaning is provided, which essentially consists exclusively of active substance.
  • soluble builder substances allows the traces introduced into the raw materials to be bound to water and thus to stabilize the bleach system and, if present, also the enzymes and / or the dirt-repellent polymers.
  • the anionic surfactants contained according to the invention can also contribute to better dispersion of the bleaching agents.
  • the fatty alkyl sulfate and / or the fatty acid soap added according to the invention has the effect that a stable matrix can be built up for the dispersion of the bleaching agent system.
  • the fatty acid monoesters and / or soaps contribute to the washing performance of the agent.
  • the soluble builders can reduce the frequently observed gel formation described above in liquid detergents or cleaning agents and can reduce the yield point and zero shear viscosity. This improves the solubility of the agent according to the invention, which leads to an overall improved washing and cleaning performance.
  • a further finding is that soluble builders contribute less than insoluble zeolites or phosphates to increasing the viscosity of the detergent or cleaning agent composition, so that larger amounts of solid bleaching agent can be incorporated.
  • the zero shear viscosity of the compositions according to the invention is still high enough to prevent sedimentation of the solid particles.
  • Another object of the present invention is a process for the production of a non-aqueous, liquid detergent or cleaner which comprises more than 20 to less than 78% by weight of nonionic surfactants, 0.1 to 25% by weight of anionic Contains surfactants, 1 to less than 20% by weight of water-soluble builder substance and more than 20 to 35% by weight of bleaching agent, which is characterized in that the solids or portions thereof contain the nonionic surfactants or Parts of it are premixed and ground in such a way that the temperature of the mixture does not exceed 45 ° C.
  • the solid particles to be used such as builder substance and bleaching agent
  • the mixture can be obtained as a stable dispersion after grinding.
  • the temperature of the mixture should not exceed 35 ° C.
  • non-aqueous means that the agent produced preferably contains no free water which is not bound as water of crystallization or in a comparable form in order to prevent decomposition of the peroxide bleaching agent.
  • small amounts of free water are tolerable, especially in amounts up to 5% by weight, the ratio of bleach to free water should be at least 3: 1.
  • the agent according to the invention contains more than 20% by weight to less than 78% by weight, preferably 30% by weight to 60% by weight, of nonionic surfactants.
  • Preferred nonionic surfactants are alkoxylated, in particular 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 are described, for example, in Japanese patent application JP 58/217598 or preferably according to that in the international patent application W0-A-90/13533 can be used.
  • liquid, alkoxylated, preferably ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms (alkyl polyglycol ether) and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol are used, in which the alcohol radical is linear or in the 2-position May be methyl-branched, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates are included linear residues from alcohols of native origin with 8 to 18 carbon atoms are preferred, for example from coconut, tallow or oleyl alcohol, which can have an average of 2 to 8 EO units per mole of alcohol.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO units or 7 EO units, Cg-Cn alcohols with 3 EO units, 5 EO units or 7 EO units, Cn-Ci5 alcohols with 5 EO units or 7 EO units and mixtures thereof, such as mixtures of Ci2-Ci4 alcohol with 3 EO units and Ci2-Ci8 alcohol with 5 EO units.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol alkoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • the agent according to the invention can contain alkyl polyglycosides, fatty acid alkyl esters and polyhydroxy fatty acid amides as further nonionic surfactants.
  • the agent according to the invention further contains 0.5 to 25% by weight, preferably 1 to 15% by weight, particularly preferably 4 to 12% by weight, of anionic surfactants.
  • C6-C22-alkyl sulfates, Cß-Ciß-alkanesulfonates, alkylbenzenesulfonates and / or fatty acid soaps are preferably used.
  • Suitable alkyl sulfates are in particular the sulfuric acid monoesters of the C6-C6b fatty alcohols, such as octyl, lauryl, myristyl, cetyl or stearyl alcohol or the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which also contain proportions of unsaturated alcohols, e.g. of oleyl alcohol.
  • Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, C8-Ci8-alkanesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates as well as disulfonates, such as those obtained from Ci2-Ci8-alkanes or Ci2-Ci8- Monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products are considered.
  • Soaps which are counted among the anionic surfactants in the context of this application are, in particular, saturated fatty acid soaps, the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, for example capronic, caprylic, coconut, palm kernel or Taig fatty acids, derived soap mixtures, suitable.
  • the agent according to the invention can contain, as further anionic surfactants, Co-Ci ⁇ -alkyl polyglycol ether sulfonates, glycerol ether sulfonates, glycerol ether sulfates, hydroxy mixed ether sulfates, monoglyceride sulfates, sulfosuccinates, sulfotriglycerides, acidic acids, Co-Ci ⁇ fatty acid amide ethersulfate, carboxylates, carböisate carbates -Cö-Ciö-Acyl-Sarcosinate, N-Cß-Cis-Acyl-Tauride, Cö-Ci ⁇ -Alkyloligoglycosidsulfate, Cö-Ciß-Al l-phosphates and mixtures thereof.
  • anionic surfactants Co-Ci ⁇ -alkyl polyglycol ether sulfonates, g
  • Sulfuric acid monoesters and the soaps can be present, for example, in total in an amount of 1 to 15% by weight, in particular 1 to 10% by weight, alone or in any mixtures in the composition according to the invention.
  • the agent according to the invention contains no other anionic surfactants besides the soaps.
  • the agent according to the invention also contains 1 to less than 20% by weight, preferably 8 to less than 20% by weight, of water-soluble builder.
  • All water-soluble organic and inorganic builder substances are suitable as builder substances.
  • Usable organic builder substances are, for example, mono and / or polycarboxylates, preferably the 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), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Particularly preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof, sodium citrate being particularly preferred.
  • the inorganic builder substances include, in particular, crystalline, layered sodium silicates of the general formula (I) NaMSi x ⁇ 2 ⁇ + i * yH2 ⁇ , 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 are preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3.
  • Layered silicates of natural and synthetic origin can also be used.
  • Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405.
  • Their usability is not limited to a special composition or structural formula.
  • smectites, in particular bentonites, are preferred here.
  • Suitable builder substances are, for example, amorphous silicates with a low water content, preferably with a water content below 15% by weight, and silicates in compound form, for example soda / silicate compounds.
  • the agent according to the invention contains, as a builder, a mixture of mono- and / or polycarboxylates and crystalline, layered sodium silicates of the general formula (I) NaMSi x 02 ⁇ + i'yH20, 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, and / or amorphous silicates.
  • the mono- and / or polycarboxylates and the crystalline phyllosilicates are preferably in a ratio of 4: 1 to 1: 4, preferably 3: 1 to 1: 3 and particularly preferably 1.2: 1 to 1: 1, 2 before.
  • the agent according to the invention contains bleaching agents in an amount of over 20 to 35% by weight, preferably over 20 to 30% by weight.
  • bleaching agents in an amount of over 20 to 35% by weight, preferably over 20 to 30% by weight.
  • the sodium borates in particular the 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 solids contained such as the builders and the bleaching agent, have a particle size distribution, so that at least 90% of the particles are smaller than 15 ⁇ m and in particular smaller than 10 ⁇ m, but at most 75% and in particular 70% of the particles are smaller than 5 ⁇ m.
  • bleach activators can be incorporated into the detergents according to the invention.
  • these are the N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight, and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED) and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triacin (DAHT).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DAHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triacin
  • the agent according to the invention contains enzymes. Their proportion can be 0.2 to 4% by weight. Enzymes from the class of proteases, lipases, amylases and cellulases or their mixtures are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtiles, Bacillus licheniformes and Streptomyces griseus are particularly suitable. The enzymes can be adsorbed onto carriers and / or embedded in coating substances in a manner known per se.
  • the agent according to the invention can additionally contain stabilizers for the enzymes.
  • stabilizers which are also suitable as stabilizers for per compounds are the salts of polyphosphonic acids, in particular l-hydroxyethane-1,1-diphosphonic acid (HEDP).
  • HEDP l-hydroxyethane-1,1-diphosphonic acid
  • the polyphosphonic acids mentioned above are also suitable for tracing Bind heavy metal.
  • suitable complexing agents for heavy metals are the above-mentioned HEDP and ethylenetriaminepentamethylenephosphonic acid (DTPMP).
  • the agent according to the invention can also contain dirt-removing polymers.
  • the dirt-removing polymers are preferably present in an amount of from 0.01% by weight to 5% by weight, preferably from 0.05% by weight to about 3% by weight.
  • polyethylene oxides with a molecular weight between 3000 and 600000 are suitable.
  • Preferred dirt-releasing polymers are those polymers which contain ethylene glycol terephthalate groups and polyethylene glycol terephthalate groups, each having 17 to 110 ethylene glycol groups, the molar ratio of ethylene glycol terephthalate to polyethylene glycol terephthalate in the polymer being from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units is in the range from 750 to 5000.
  • the polymers can have an average molecular weight from approximately 5000 to approximately 200000.
  • Ethylene glycol terephthalate and polyethylene glycol terephthalate may be distributed arbitrarily in the polymer.
  • Preferred polymers are those with molar ratios of ethylene glycol terephthalate / polyethylene glycol terephthalate from 65:35 to 90:10, preferably from 65:35 to 80:20, the linking polyethylene glycol units having a molecular weight of 750 to 5000, preferably 1000 to 3000 and the polymer a molecular weight from 10,000 to 50,000.
  • An example of commercially available polymers of this type is the product sold under the trade name "Repel-0-Tex SRP3" by Rhone-Poulenc, France.
  • the dirt-removing polymers which are preferably used can be prepared by known polymerization processes, the starting materials being used in amounts such as to obtain the above-mentioned ratios of ethylene glycol terephthalate to polyethylene glycol terephthalate.
  • the processes described in US Pat. No. 3,479,212 can be used to produce suitable polymers.
  • further inorganic substances can be used in the agents according to the invention. Alkali carbonates, for example soda, alkali hydrogen carbonates, alkali sulfates, phosphates, can be mentioned as suitable substances in this connection.
  • Such additional inorganic material can be contained in amounts up to 10 wt .-%.
  • the agents according to the invention can contain optical brighteners and graying inhibitors, foam inhibitors, and colorants and fragrances as further constituents.
  • the yield point tp at 20 ° C is 0.5 to 10 Pa, preferably 1 to 5 Pa.
  • the agent according to the invention preferably contains no solvents.
  • the agent according to the invention contains an active substance content of 100%.
  • the pH of the compositions is preferably between 7 and 11 and preferably between 8.5 and 10.5.
  • agents according to the invention can be used in detergents as well as in cleaning agents.
  • agents of high viscosity according to the invention can be used in commercial textile cleaning.
  • the solids or portions thereof are premixed with the nonionic surfactants or portions thereof and ground in such a way that the temperature of the mixture does not exceed 45 ° C., preferably 40 ° C. and in particular 35 ° C.
  • part of the total amount of solids or of the total nonionic liquid surfactants means that the total amount of a single component, eg. B. builders or bleaches, as part of the total solids or nonionic liquid surfactants.
  • the ground portions and optionally other components can then be mixed to the desired recipe.
  • the solid particles of the non-aqueous liquid prepared according to the invention preferably have
  • all components of the agent according to the invention are premixed to form a grinding batch and then ground in one pass (passage) through a grinding device to the desired particle size distribution.
  • a procedure is particularly advantageous if the solid particles are smaller than 1.0 mm, preferably smaller than 0.8 mm.
  • the premix can either be passed through the same grinding device in several passages (discontinuous grinding) or the mixture can be ground to the required fineness in a multi-stage grinding in a continuous pass through grinding devices connected in series.
  • discontinuous grinding three-pass grinding, in particular two-pass grinding, is preferred.
  • multistage continuous grinding three, particularly preferably two, grinding devices are preferably arranged one behind the other.
  • the mixture pre-grind to a particle size in the first grinding, ie in the first passage or in the first stage, so that about 90% of the particles have a particle size smaller than 100 ⁇ m, preferably smaller than 50 ⁇ m.
  • the particles can then be placed in one or several further grinding stages are ground to the desired particle size distribution.
  • the solid particles without enzymes are premixed with a partial amount of the liquid nonionic surfactants and the enzymes are premixed with a further partial amount of the liquid nonionic surfactants and ground separately in a so-called partial current milling.
  • the grinding batches are then mixed, if appropriate with further components which have not been ground, to give the desired recipe.
  • the enzymes can be used as granules, but in particular as a liquid enzyme formulation.
  • a viscous dispersion is obtained.
  • shear forces that increase the energy density in the dispersion and lead to heating. The higher the shear forces, the greater the warming.
  • the size of the shear forces that occur is u. a. determined by the size of the grinding chamber and its filling. Heating of the ground material can be avoided by directly dissipating the heat that occurs and / or by working with low shear forces.
  • the grinding chamber is delimited by large cooling surfaces, to which the heat that is generated is released. It is preferred that the grinding chamber is surrounded by a cooling medium so that the heat that is generated is released to the surface of the grinding chamber and is transferred from there to a cooling medium.
  • the heat transfer is the more effective the higher the thermal conductivity of the material with which the surface of the grinding chamber is lined or the larger the surface of the grinding chamber.
  • the temperature of the cooling medium generally depends on the thermal conductivity of the material with which the grinding chamber is equipped. The higher the thermal conductivity of the material in the grinding chamber, the higher the temperature of the cooling medium can be. It should be noted that the temperature of the cooling medium is not too low.
  • the fixed point of the suspension according to the invention is usually from 0 to 15 ° C.
  • the cooling medium there is a risk that the wall of the grinding chamber becomes too cold, so that the temperature of the mixture to be milled is selectively below the melting point on the surface of the wall of the grinding chamber.
  • This substance which is still viscous to solid, can stick there and form a boundary layer, which can hinder heat dissipation and lead to unsatisfactory grinding.
  • the material forming this boundary layer no longer effectively participates in the milling process.
  • the size of the grinding chamber, the filling quantity of the grinding balls, the material of the grinding chamber wall and the temperature and type of cooling medium are matched to one another in such a way that the composition to be milled is adjusted to the desired particle size distribution in an economically acceptable time or with a high grinding material throughput is ground without the temperature of the dispersion exceeding 45 ° C., preferably 40 ° C. and in particular 35 ° C.
  • the premix is preferably ground using wet ball mills or roller mills. Agitator ball mills and annular gap ball mills with as narrow a grinding chamber as possible and a large cooling surface are particularly preferred.
  • the ratio of the drive power acting on the grinding rotor to the regrind throughput in these mills should be greater than 0.001 kWh / kg, preferably greater than 0.05 kWh / kg and in particular greater than 0.125 kWh / kg.
  • the surfaces of the parts of the mill that come into contact with the product must be sufficiently harder than the materials to be ground. Suitable materials are therefore, for example, chilled cast iron, steel, hardened steel and hardened stainless steel. Furthermore, the mill parts with hard metals or Ceramic materials are coated, such as alumina or silicon carbide ceramic.
  • the anionic surfactant was dissolved in the nonionic surfactants at 90 ° C and then cooled to room temperature.
  • the product was then wet-ground in a cooled ball mill (zirconium oxide balls, diameter 1.2 to 1.6 mm, maximum temperature ⁇ 35 ° C.).
  • APG soda compound 14 8.0 8.0 -
  • Dehydol ( R ) LT7 is an ethoxylated Ci2-Ci8 fatty alcohol with an average of 7 EO units (commercial product from Henkel, Düsseldorf)
  • Dehydol ( R ) LST 80/20 is a mixture of 80% of an ethoxylated Ci2-Ci8 ⁇ fatty alcohol with an average of 5 EO units and 20% of an ethoxylated Ci2 _ Ci4-fatty alcohol with an average of 3 EO units (commercial product from Henkel, Düsseldorf).
  • Lutensol ( R ) is an ethoxylated Ci2-Ci5-0xofetal alcohol with an average of 7 EO units (commercial product from BASF, Ludwigshafen)
  • Maranil ( R ) A is a C 1 -C 3 -alkylbenzenesulfonate (commercial product from Hüls, Mari)
  • Sulfopon ( R ) T is a Ci6-Ci8 fatty alcohol sulfate (commercial product from Henkel, Düsseldorf)
  • Edenor ( R ) HT 35 is a Ci5-Ci8 fatty acid soap (commercial product from Henkel, Düsseldorf)
  • SKS-6 is a crystalline layered silicate from Hoechst, Frankfurt
  • VP 1132 is a silicone oil (commercial product from Dow Corning)
  • Turpinal ( R ) 2 NZ is a hydroxyethyl diphosphonate (commercial product from Henkel, Düsseldorf)
  • BLAP ( R ) 140 is a protease (commercial product from Henkel, Düsseldorf)
  • Examples 7-9 are suitable both for textile washing and in particular for cleaning hard surfaces.
  • Table 3 shows the good storage stability of the formulations 5 and -6 according to the invention at room temperature and elevated temperature over a long period of time.

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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

Des produits de lavage ou de nettoyage contenant des solides et des agents de blanchiment sont stables au stockage lorsqu'ils ne sont pas aqueux et qu'ils contiennent entre 20 et 78 % en poids d'agents tensioactifs non ioniques, 0,1 à 25 % en poids d'agents tensioactifs anioniques, 1 à 20 % en poids d'adjuvants solubles dans l'eau et 20 à 35 % en poids d'agents de blanchiment. Ces produits peuvent en outre contenir des enzymes et des polymères antisalissants. On prépare ces produits en mélangeant au préalable les agents tensioactifs ou des quantités partielles de ceux-ci et en les broyant de sorte que la température du mélange ne dépasse pas 45 DEG C.
EP95930440A 1994-08-16 1995-08-07 Produit liquide de lavage ou de nettoyage a pouvoir blanchissant Expired - Lifetime EP0777722B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4428958 1994-08-16
DE19944428958 DE4428958A1 (de) 1994-08-16 1994-08-16 Flüssigwaschmittel mit Bleiche
DE4436151A DE4436151A1 (de) 1994-08-16 1994-10-11 Verfahren zur Herstellung eines Flüssigwaschmittels mit Bleiche
DE4436151 1994-10-11
PCT/EP1995/003124 WO1996005284A1 (fr) 1994-08-16 1995-08-07 Produit liquide de lavage ou de nettoyage a pouvoir blanchissant

Publications (2)

Publication Number Publication Date
EP0777722A1 true EP0777722A1 (fr) 1997-06-11
EP0777722B1 EP0777722B1 (fr) 1999-03-17

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EP95930440A Expired - Lifetime EP0777722B1 (fr) 1994-08-16 1995-08-07 Produit liquide de lavage ou de nettoyage a pouvoir blanchissant

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US (1) US5880083A (fr)
EP (1) EP0777722B1 (fr)
JP (1) JPH10504342A (fr)
KR (1) KR100383832B1 (fr)
CN (1) CN1113957C (fr)
AT (1) ATE177779T1 (fr)
DE (2) DE4436151A1 (fr)
ES (1) ES2130641T3 (fr)
WO (1) WO1996005284A1 (fr)

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE508150C2 (sv) 1996-08-30 1998-09-07 Sandvik Ab Förfarande för att tillverka band av ferritiskt, rostfritt FeCrAl-stål
DE19725508A1 (de) 1997-06-17 1998-12-24 Clariant Gmbh Wasch- und Reinigungsmittel
CN1145690C (zh) * 1997-06-27 2004-04-14 普罗格特-甘布尔公司 含漂白剂的含颗粒的非水基洗涤剂组合物
DE19850223A1 (de) * 1998-10-31 2000-05-04 Clariant Gmbh Wasch- und Reinigungsmittel enthaltend alkoxylierte Fettsäurealkylester
DE19854960A1 (de) 1998-11-29 2000-05-31 Clariant Gmbh Maschinengeschirrspülmittel
DE10011273A1 (de) * 2000-03-08 2001-09-20 Henkel Kgaa Flüssigwaschmittel mit flüssigen Bleichaktivatoren
DE10131721C1 (de) * 2001-06-30 2003-03-13 Henkel Kgaa Schnell lösliches Reinigungsgel
DE102006055669A1 (de) * 2006-11-23 2008-07-17 Henkel Kgaa Enzymzubereitung mit trägergebundenen Antioxidationsmitteln
US8026040B2 (en) 2007-02-20 2011-09-27 Az Electronic Materials Usa Corp. Silicone coating composition
JP5331412B2 (ja) * 2007-12-28 2013-10-30 ライオン株式会社 液体洗浄剤組成物
US8877254B2 (en) 2010-12-29 2014-11-04 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
PL2687094T3 (pl) 2010-12-29 2018-09-28 Ecolab Usa Inc. Wytwarzanie kwasów peroksykarboksylowych w zasadowym pH i ich zastosowanie jako czynniki wybielające tekstylia i czynniki przeciwmikrobiologiczne
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
DE102012204270A1 (de) 2012-03-19 2013-09-19 Henkel Ag & Co. Kgaa Flüssiges Waschmittel mit erhöhter Reinigungsleistung
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
WO2014105366A1 (fr) * 2012-12-28 2014-07-03 The Dial Corporation Détergents pour le lavage du linge et procédés de fabrication de détergents pour le lavage du linge contenant des éthoxylates d'ester méthylique
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US20140256811A1 (en) 2013-03-05 2014-09-11 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
ES2726813T3 (es) 2013-03-25 2019-10-09 Ecolab Usa Inc Composición de detergente líquida
BR112016010950B1 (pt) 2013-11-22 2020-03-10 Colgate-Palmolive Company Composição que é um sabonete líquido para as mãos ou para lavagem do corpo
GB201414179D0 (en) * 2014-08-11 2014-09-24 Reckitt Benckiser Brands Ltd Detergent
US11026552B2 (en) 2016-01-19 2021-06-08 3M Innovative Properties Company Consumer scrubbing article with stain release and method of making same
MX2021008789A (es) 2019-01-22 2021-08-24 Ecolab Usa Inc Mezcla de polimeros para estabilizar detergente de lavanderia altamente alcalino.
EP3931292A1 (fr) 2019-02-28 2022-01-05 Ecolab USA Inc. Système de stabilisation pour émulsions de blanchisserie

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1119368A (en) * 1964-07-22 1968-07-10 Ici Ltd Polyester-polyoxyalkylene block or graft copolymer composition
GB1114359A (en) * 1965-11-29 1968-05-22 Witco Chemical Corp Improvements in or relating to liquid detergent compositions
ZA734721B (en) * 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
GB1600981A (en) * 1977-06-09 1981-10-21 Ici Ltd Detergent composition
EP0026529B2 (fr) * 1979-09-29 1992-08-19 THE PROCTER & GAMBLE COMPANY Compositions détergentes
DE3065199D1 (en) * 1979-12-04 1983-11-10 Ici Plc Detergent composition
JPS58217598A (ja) * 1982-06-10 1983-12-17 日本油脂株式会社 洗剤組成物
US5362413A (en) * 1984-03-23 1994-11-08 The Clorox Company Low-temperature-effective detergent compositions and delivery systems therefor
EG16786A (en) * 1984-03-23 1991-08-30 Clorox Co Low-temperature effective composition and delivery systems therefor
DE3413571A1 (de) * 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3526405A1 (de) * 1985-07-24 1987-02-05 Henkel Kgaa Schichtsilikate mit beschraenktem quellvermoegen, verfahren zu ihrer herstellung und ihre verwendung in wasch- und reinigungsmitteln
US4846992A (en) * 1987-06-17 1989-07-11 Colgate-Palmolive Company Built thickened stable non-aqueous cleaning composition and method of use, and package therefor
NZ216987A (en) * 1985-08-20 1988-09-29 Colgate Palmolive Co Nonaqueous liquid low phosphate laundry detergent
US4655954A (en) * 1985-08-20 1987-04-07 Colgate-Palmolive Company Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
DE3621536A1 (de) * 1986-06-27 1988-01-07 Henkel Kgaa Fluessiges waschmittel und verfahren zu seiner herstellung
NZ221506A (en) * 1986-08-28 1989-08-29 Colgate Palmolive Co Fabric-treating detergent composition with a suspension of insoluble inorganic particles
DE3914131A1 (de) * 1989-04-28 1990-10-31 Henkel Kgaa Verwendung von calcinierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung von fettsaeureestern
NZ238047A (en) * 1990-05-07 1993-12-23 Colgate Palmolive Co Nonaqueous liquid automatic dihwashing detergent comprising silica,
DE4024531A1 (de) * 1990-08-02 1992-02-06 Henkel Kgaa Fluessigwaschmittel
DE4216453A1 (de) * 1992-05-19 1993-11-25 Henkel Kgaa Verfahren zur Herstellung pastenförmiger Waschmittel
CA2139674A1 (fr) * 1992-07-08 1994-01-20 Mark P. Houghton Produits de nettoyage liquides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9605284A1 *

Also Published As

Publication number Publication date
CN1113957C (zh) 2003-07-09
US5880083A (en) 1999-03-09
DE4436151A1 (de) 1996-05-02
WO1996005284A1 (fr) 1996-02-22
EP0777722B1 (fr) 1999-03-17
CN1155298A (zh) 1997-07-23
DE59505389D1 (de) 1999-04-22
ATE177779T1 (de) 1999-04-15
KR970704869A (ko) 1997-09-06
KR100383832B1 (ko) 2003-07-16
JPH10504342A (ja) 1998-04-28
ES2130641T3 (es) 1999-07-01

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