EP0777722B1 - Produit liquide de lavage ou de nettoyage a pouvoir blanchissant - Google Patents

Produit liquide de lavage ou de nettoyage a pouvoir blanchissant Download PDF

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Publication number
EP0777722B1
EP0777722B1 EP95930440A EP95930440A EP0777722B1 EP 0777722 B1 EP0777722 B1 EP 0777722B1 EP 95930440 A EP95930440 A EP 95930440A EP 95930440 A EP95930440 A EP 95930440A EP 0777722 B1 EP0777722 B1 EP 0777722B1
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EP
European Patent Office
Prior art keywords
weight
formulation
mixture
enzymes
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.)
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EP95930440A
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German (de)
English (en)
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EP0777722A1 (fr
Inventor
Hans-Josef Beaujean
Christian Block
Rainer Hofmann
Dieter Legel
Rudolf Lind
Josef Penninger
Bernd Richter
Reiner Schackmann
Karl Schwadtke
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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
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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 is non-ionic and anionic Contains surfactants and builders, and a process for their preparation Means.
  • aqueous washing and cleaning agents contain anionic ones and nonionic surfactants.
  • bleach systems it has proven to be very difficult proven to incorporate bleach systems into these agents. In practice is therefore often used in these agents on the use of bleach systems waived, which leads to a reduction in washing performance bleachable stains.
  • Some liquid detergents available on the market contain very special bleach systems, however either have very low oxidation potentials or are unstable and disintegrate even with short storage times, which does not improve the washing activity with bleachable stains.
  • liquid detergent compositions are found in the literature described, which may contain bleach.
  • non-aqueous Known liquid detergent from liquid nonionic surfactants the 20 to 70 wt .-% builder substances and 1 to 20 wt .-% bleach in may contain suspended form.
  • anionic surfactants such as alkylbenzenesulfonates, olefin sulfonates, Alkyl sulfates or soap, optical brighteners, dyes, fragrances or Enzymes can be added.
  • EP-B-0 460 810 describes a non-aqueous, liquid detergent composition for dishwashers that use a non-aqueous, organic carrier liquid and at least one component selected from organic detergent, detergent builder, Foam inhibitor and mixtures thereof and a component selected from a non-abrasive amount of 0.5 to 10% of small, in essential water-insoluble particles of silicon dioxide, aluminum oxide or contains titanium oxide or mixtures thereof as an anti-film-forming agent.
  • the agent described can also contain 3 to 15% by weight of bleach contain.
  • WO 94/01524 describes an essentially non-aqueous liquid detergent described that in addition to nonionic surfactant up to 60 wt .-% Builder substance and contains between 5 and 35 wt .-% bleach.
  • the liquid detergent composition described also contains one Polymer compound, the viscosity of the dispersion of the solid Builder substances and bleach in nonionic surfactant reduced to to obtain a flowable and pourable composition.
  • liquid detergents containing bleach are obtained when the bleach is in the form of a stable dispersion.
  • the commercially available and from the above Known liquid detergents have the disadvantage that for Maintaining a stable dispersion requires additional auxiliaries.
  • the dispersion in the commercial liquid detergents only is a limited stable dispersion, it is not possible in these products side by side to incorporate bleach and enzymes because the Bleach destroys enzymes.
  • liquid detergents containing bleach for washing or cleaning is another difficulty.
  • Stable dispersions the solid particles in the liquid phase are usually obtained when the solid particles have a small particle size and narrow Have particle size distribution. Because of the different manufacturing processes is the particle size of the builder particles and the Bleach particles very different, resulting in a very broad Particle size distribution leads. In particular solid particles with large Diameters lead to unstable dispersions.
  • the present invention has for its object to provide a stable, To provide a liquid detergent containing bleach for washing and cleaning, which is the solid bleach in the form of a stable dispersion contains, even if stored for a long period without affecting the activity of the substances it contains and which also components sensitive to bleach may contain. Another object of the invention is a method to provide for the preparation of these agents.
  • the present invention relates to a non-aqueous liquid detergent for washing or cleaning containing a maximum of 5% by weight of free water, which comprises more than 20 to less than 78% by weight of nonionic surfactants, 0.1 to 4% by weight.
  • % anionic surfactants selected from the group consisting of C 6 -C 22 alkyl sulfates, C 8 -C 18 alkanesulfonates. Alkylbenzenesulfonates and / or fatty acid soaps, 1 to less than 20% by weight of water-soluble builder substance and more than 20 to 35% by weight of bleaching agent.
  • the agent according to the invention is a special one Combination of active washing or cleaning ingredients contains, which creates a flowable and storage-stable liquid is provided for washing and cleaning, which essentially consists exclusively of active substance.
  • active washing or cleaning ingredients contains, which creates a flowable and storage-stable liquid is provided for washing and cleaning, which essentially consists exclusively of active substance.
  • Studies have shown that through the use of soluble builder substances the over the raw material traces bound to water and thus a stabilization the bleach system and, if available, the enzymes and / or the dirt-repellent polymers can be achieved.
  • the Anionic surfactants contained according to the invention can for better Dispersion of the bleaching agents contribute.
  • soluble builders are those described above, frequently observed gel formation in liquid washing or cleaning agents and the yield point and zero shear viscosity can be reduced. This improves the solubility of the agent according to the invention, which leads to an overall improved washing or cleaning performance.
  • a Another finding is that soluble builders are less than insoluble ones Zeolites or phosphates to increase the viscosity of the detergent or cleaning agent composition contribute so that larger amounts of solid Bleach can be incorporated.
  • Zero shear viscosity of the compositions according to the invention still high enough to prevent sedimentation of the solid particles.
  • Another object of the present invention is a method for producing a non-aqueous, liquid detergent or cleaning agent which contains more than 20 to less than 78% by weight of nonionic surfactants, 0.1 to 4% by weight of anionic surfactants, selected from the group consisting of C 6 -C 22 alkyl sulfates, C 8 -C 18 alkanesulfonates, alkylbenzenesulfonates and / or fatty acid soaps, 1 to less than 20% by weight of water-soluble builder substance and more than 20 to 35% by weight of bleach contains claimed, which is characterized in that the solids or portions thereof are premixed with the nonionic surfactants or portions thereof and ground such that the temperature of the mixture does not exceed 45 ° C.
  • the solid particles to be used such as Builder substance and bleach
  • the temperature of the mixture should be 35 ° C do not exceed.
  • non-aqueous means that the product produced Means preferably no free, not as crystal water or comparable Form bound water contains to decompose the peroxide bleach to prevent. In some cases, small amounts are available free water tolerable, especially in amounts up to 5% by weight, whereby the ratio of bleach to free water is at least 3: 1 should.
  • 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.
  • nonionic surfactants are preferably alkoxylated, in particular 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 described, for example, in the Japanese patent application JP 58/217598 are described or preferably according to the in of the international patent application WO-A-90/13533 are produced, 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 (EO) per mole of alcohol are used, in which the alcohol residue is linear or methyl-branched in the 2-position may, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 E0 units or 7 E0 units, C 9 -C 11 alcohols with 3 E0 units, 5 E0 units or 7 E0 units, C 11 -C 15 alcohols with 5 E0 units or 7 E0 units and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 units and C 12 -C 18 alcohol with 5 E0 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 be used as further nonionic surfactants
  • Alkyl polyglycosides, fatty acid alkyl esters and polyhydroxy fatty acid amides contain.
  • the agent according to the invention further contains 0.1 to 4% by weight of anionic surfactants from the group of the C 6 -C 22 alkyl sulfates, C 8 -C 18 alkanesulfonates, alkylbenzenesulfonates and / or fatty acid soaps.
  • Particularly suitable alkyl sulfates are the sulfuric acid monoesters of the C 6 -C 18 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 additionally contain proportions of unsaturated alcohols, eg oleyl alcohol.
  • Suitable surfactants of the sulfonate type are C 8 -C 18 alkanesulfonates and preferably C 9 -C 13 alkylbenzenesulfonates, and also disulfonates of the type obtained, for example, from C 12 -C 18 alkanes or C 12 -C 18 monoolefins - Or internal double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • soaps included in the scope of this application for the anionic surfactants are particularly saturated fatty acid soaps, the salts lauric acid, myristic acid, palmitic acid or stearic acid, and especially from natural fatty acids, e.g. Capron, Capryl, Coconut, Palm kernel or tallow fatty acids, derived soap mixtures, suitable.
  • the agent according to the invention contains besides the soaps, no other anionic surfactants.
  • 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), provided that such use is not objectionable for ecological reasons is, 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 of these, sodium citrate being particularly preferred.
  • the inorganic builder substances are crystalline, layered sodium silicates of the general formula (I) NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application 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.
  • M represents sodium
  • x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • layered silicates can be of natural and synthetic origin be used.
  • Layered silicates of this type are known, for example, from US Pat Patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405 are known. Their usability is not due to a special composition or structural formula limited. However, smectites are preferred here, in particular Bentonite.
  • 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 O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is one 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 present 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 .
  • 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.
  • sodium borates in particular sodium perborate tetrahydrate and sodium perborate monohydrate, are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the solids contained, such as Builder and the bleach 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 0-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activators contain bleach activators 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-triacine (DAHT).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DAHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triacine
  • the agent according to the invention contains in a preferred embodiment Enzymes. Their proportion can be 0.2 to 4% by weight. Coming as enzymes those from the class of proteases, lipases, amylases and cellulases or their mixtures in question. Bacterial strains are particularly suitable or mushrooms such as Bacillus subtiles, Bacillus licheniformes and Streptomyces griseus-derived enzymatic agents. The enzymes can in adsorbed in a known manner on carriers and / or in coating substances be embedded.
  • the agent according to the invention can additionally stabilizers for the enzymes contain.
  • stabilizers also as stabilizers for per compounds the salts of polyphosphonic acids are particularly suitable 1-hydroxyethane-1,1-diphosphonic acid (HEDP) into consideration.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • the above mentioned polyphosphonic acids are also suitable for traces of Bind heavy metal.
  • a suitable complexing agent for heavy metals are for example the above-mentioned HEDP and the ethylenetriaminepentamethylenephosphonic acid (DTPMP) suitable.
  • the agent according to the invention can furthermore contain dirt-removing polymers.
  • the soil release polymers are preferred in an amount of 0.01 to 5 wt .-%, preferably 0.05 wt .-% to about 3 wt .-%.
  • polyethylene oxides with a molecular weight are suitable between 3000 and 600000.
  • Preferred soil release polymers are those polymers which have ethylene glycol terephthalate groups and polyethylene glycol terephthalate groups, the each contain from 17 to 110 ethylene glycol groups, the Molar ratio of ethylene glycol terephthalate to polyethylene glycol terephthalate in the polymer is from 50:50 to 90:10. In these connections is the molecular weight of the linking polyethylene glycol units in the range of 750 to 5000.
  • the polymers can have an average Have molecular weights from about 5,000 to about 200,000. in the Polymer can include ethylene glycol terephthalate and polyethylene glycol terephthalate arbitrarily distributed.
  • 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 a molecular weight of 750 to 5000, preferably 1000 to 3000 and that Polymers has a molecular weight of 10,000 to 50,000.
  • the preferred dirt-removing polymers can be known Polymerization processes are prepared using the starting materials be used in such amounts to the above Ratios of ethylene glycol terephthalate to polyethylene glycol terephthalate to obtain. For example, those described in U.S. Patent No. 3,479,212 Processes for the production of suitable polymers can be used.
  • alkali metal carbonates e.g. Soda
  • alkali hydrogen carbonates alkali sulfates
  • phosphates phosphates to be named.
  • additional inorganic material can in Amounts up to 10 wt .-% may be included.
  • the agents according to the invention can be optical components Brighteners and graying inhibitors, foam inhibitors, and color and Contain fragrances.
  • the yield point t F is 0.5 to 10 Pa, preferably 1 to 5 Pa at 20 ° C.
  • the agent according to the invention preferably contains no solvents.
  • the invention Agent has 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.
  • the agents according to the invention can be used both in detergents and in cleaning agents be used.
  • Agents with high viscosity used in commercial textile cleaning become.
  • part of the total amount of solids means or the total nonionic liquid surfactants, being a subset also the total amount of a single component, e.g. B. Builder or Bleach, as part of the total solids or non-ionic liquid Can mean surfactants.
  • the ground portions and if necessary further components can then be mixed to the desired recipe become.
  • the solid particles preferably have those prepared according to the invention non-aqueous liquid Using a particle size distribution that at least 90% of the particles smaller than 10 ⁇ m and at most 70% of the particles smaller than 5 ⁇ m are.
  • all components of the invention Premixed to a batch and then in one pass (Passage) through a grinding device to the desired particle size distribution grind.
  • Passage through a grinding device to the desired particle size distribution grind.
  • the solids contain particles with a very broad particle size distribution or particle sizes larger than 1.0 mm, z. B. enzymes in granular form, so the premix can either pass through the same in several passages Grinding device performed (discontinuous grinding) or the mixture can be carried out in a multi-stage grinding in a continuous pass successive grinding devices to the required fineness be ground.
  • discontinuous grinding is a three-pass grinding, in particular a two-pass grinding is preferred.
  • At a multi-stage continuous grinding are preferably three, especially preferably two grinding devices arranged one behind the other.
  • the mixture in the first grinding i.e. in the first passage or pre-grind to a particle size 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 to the desired particle size distribution be ground.
  • the Enzymes for incorporation into the liquid detergent according to the invention, the Enzymes as granules, but especially as a liquid enzyme formulation be used.
  • the grinding room is large Limited cooling surfaces to which the heat is given off. It is preferred that the grinding chamber is surrounded by a cooling medium, so that the any heat generated is released to the surface of the grinding chamber and from there is transferred to a cooling medium. The heat transfer is all 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 room.
  • the temperature of the cooling medium usually depends on the thermal conductivity of the material with which the grinding chamber is equipped. The higher the thermal conductivity of the material of the grinding chamber is higher the temperature of the cooling medium. It should be noted that the Coolant temperature is not too low.
  • the benchmark of the invention Suspension is usually 0 to 15 ° C. At low Temperatures of the cooling medium there is a risk that the wall of the Grinding room is too cold, so that the temperature of the mixture to be ground selectively on the surface of the wall of the grinding chamber below of the melting point. This still viscous to solid substance can adhere there and form a boundary layer, which reduces heat dissipation hinder and lead to unsatisfactory grinding. Furthermore the material forming this boundary layer no longer effectively takes up Part of the grinding process.
  • the size of the grinding chamber, the Filling quantity of the grinding balls, the material of the grinding chamber wall and temperature and the type of cooling medium so coordinated that the grinding composition in an economically acceptable time or at high grind throughput to the desired particle size distribution is without the temperature of the dispersion 45 ° C, preferably 40 ° C. and in particular exceeds 35 ° C.
  • the ratio of the drive power acting on the grinding rotor in these mills for regrind throughput should preferably be greater than 0.001 kWh / kg be greater than 0.05 kWh / kg and in particular greater than 0.125 kWh / kg.
  • the surfaces of the parts of the mill in contact with the product must be sufficient be harder than the materials to be ground.
  • materials hence, for example, chilled cast iron, steel, hardened steel and hardened steel Stainless steel.
  • the mill parts with hard metals or Ceramic materials such as aluminum oxide or coated Silicon carbide ceramic.

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Claims (20)

  1. Produit liquide non aqueux, contenant au maximum 5 % en poids d'eau libre, pour le lavage ou le nettoyage, contenant plus de 20 à moins de 78 % en poids d'agents tensioactifs non ioniques, de 0,1 à 4 % en poids d'agents tensioactifs anioniques, choisis dans le groupe constitué par les sulfates d'alkyle en C6 à C22, les sulfonates d'alcane en C8 à C18, les sulfonates d'alkylbenzène et/ou les savons d'acides gras, de 1 à moins de 20 % en poids d'adjuvants solubles dans l'eau, et plus de 20 à 35 % en poids d'agent de blanchiment.
  2. Produit selon la revendication 1,
    caractérisé en ce que
    l'agent tensioactif non ionique est choisi dans le groupe des esters alkyliques d'acides gras alcoxylés, de préférence éthoxylés ou éthoxylés et propoxylés, de préférence ayant de 1 à 4 atomes de carbone dans le chaíne alkyle, en particulier les esters méthyliques d'acides gras.
  3. Produit selon l'une des revendications 1 à 2,
    caractérisé en ce que,
    en dehors des savons, il ne contient pas d'autres agents tensioactifs anioniques.
  4. Produit selon l'une des revendications 1 à 3,
    caractérisés en ce que
    les adjuvants solubles dans l'eau sont des polycarboxylates, de préférence les acides polycarboxyliques utilisés sous forme de leurs sels de sodium, ainsi que leurs mélanges.
  5. Produit selon la revendication 4,
    caractérisé en ce qu'
    on utilise comme adjuvants un mélange de mono- et/ou polycarboxylates et de silicates de sodium stratifiés cristallins de formule générale NaMSixO2x+1·yH2O dans laquelle M représente le sodium ou l'hydrogène, x représente un nombre entier de 1,9 à 4 et y un nombre de 0 à 20 et les valeurs préférées pour x sont 2, 3 ou 4, et/ou des silicates amorphes, où dans un mode de réalisation préféré les carboxylates monomères, oligomères et polymères et les silicates stratifiés cristallins sont présents dans un rapport de 4:1 à 1:4, en particulier de 3:1 à 1:3.
  6. Produit selon l'une des revendications 1 à 5,
    caractérisé en ce que
    l'agent de blanchiment est le perborate de sodium.
  7. Produit selon l'une des revendications 1 à 6,
    caractérisé en ce que
    les solides dispersés présentent une granulométrie telle qu'au moins 90 % des particules ont moins de 15 µm et en particulier de moins de 10 µm, mais au plus 75 % et en particulier 70 % des particules ont moins de 5 µm.
  8. Produit selon l'une des revendications 1 à 7,
    caractérisé en ce qu'
    il contient un activateur de blanchiment.
  9. Produit selon l'une des revendications 1 à 8,
    caractérisé en ce qu'
    il contient de 0,2 à 4 % en poids d'enzymes.
  10. Produit selon la revendication 9,
    caractérisé en ce que
    les enzymes sont choisis dans le groupe constitué par les classes des protéases, lipases, cellulases et amylases.
  11. Produit selon l'une des revendications 1 à 10,
    caractérisé en ce qu'
    il contient des polymères dissolvant les salissures.
  12. Procédé de fabrication d'un produit de lavage liquide non aqueux qui contient plus de 20 à moins de 78 % en poids d'agents tensioactifs non ioniques, de 0,1 à 4 % en poids d'agents tensioactifs anioniques, choisis dans le groupe constitué par les sulfates d'alkyles en C6 à C22, les sulfonates d'alcanols en C8 à C18, les sulfonates d'alkylbenzène et/ou les savons d'acides gras, de 1 à moins de 20 % en poids d'adjuvants solubles dans l'eau et plus de 20 à 35 % en poids d'agent de blanchiment,
    caractérisé en ce que
    les solides ou parties de solides contenus sont prémélangés avec les agents tensioactifs non ioniques ou des parties de ces agents tensioactifs non ioniques et broyés de manière que la température du mélange ne dépasse pas 45°C.
  13. Procédé selon la revendication 12,
    caractérisé en ce que
    la température du mélange ne dépasse pas 40°C, de préférence 35°C.
  14. Procédé selon l'une des revendications 12 ou 13,
    caractérisé en ce qu'
    on broie le prémélange en une fois.
  15. Procédé selon l'une des revendications 12 à 14,
    caractérisé en ce qu'
    on conduit le prémélange plusieurs fois à travers le même dispositif de broyage.
  16. Procédé selon l'une des revendications 12 à 15,
    caractérisé en ce qu'
    on conduit et en ce qu'on broie le prémélange à travers plusieurs dispositifs de broyage disposés les uns à la suite des autres.
  17. Procédé selon l'une des revendications 12 à 16, caractérisé en ce qu'
    on effectue le mélange avec un moulin à billes humides ou un moulin à cylindres.
  18. Procédé selon la revendication 17,
    caractérisé en ce que
    le moulin à billes humides est un moulin à billes avec agitateur présentant un étroit espace de broyage et une grande surface de refroidissement.
  19. Procédé selon l'une des revendications 12 à 18,
    caractérisé en de que
    le mélange contient des enzymes que l'on peut de préférence transformer en formulation liquide.
  20. Procédé selon la revendication 19,
    caractérisé en ce que
    l'on prémélange les particules solides sans enzymes avec une partie des agents tensioactifs non ioniques liquides et les enzymes avec une autre partie des agents tensioactifs non ioniques liquide et en ce qu'on broie les prémélanges séparément.
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 EP0777722A1 (fr) 1997-06-11
EP0777722B1 true EP0777722B1 (fr) 1999-03-17

Family

ID=25939257

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95930440A Expired - Lifetime EP0777722B1 (fr) 1994-08-16 1995-08-07 Produit liquide de lavage ou de nettoyage a pouvoir blanchissant

Country Status (9)

Country Link
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

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
EP0777722A1 (fr) 1997-06-11
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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