EP0846758A2 - Additif détergent - Google Patents

Additif détergent Download PDF

Info

Publication number
EP0846758A2
EP0846758A2 EP97121101A EP97121101A EP0846758A2 EP 0846758 A2 EP0846758 A2 EP 0846758A2 EP 97121101 A EP97121101 A EP 97121101A EP 97121101 A EP97121101 A EP 97121101A EP 0846758 A2 EP0846758 A2 EP 0846758A2
Authority
EP
European Patent Office
Prior art keywords
weight
additives
additive
acid
zeolite
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
EP97121101A
Other languages
German (de)
English (en)
Other versions
EP0846758A3 (fr
EP0846758B1 (fr
Inventor
Rene-Andres Dr. Artiga Gonzalez
Volker Dr. Bauer
Monika Dr. Böcker
Fred Dr. Schambil
Heinke Jebens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0846758A2 publication Critical patent/EP0846758A2/fr
Publication of EP0846758A3 publication Critical patent/EP0846758A3/fr
Application granted granted Critical
Publication of EP0846758B1 publication Critical patent/EP0846758B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the invention relates to an additive for use in detergents or cleaning agents, a method for its manufacture as well as detergents or cleaning agents containing these additives contain.
  • Modern powdery to granular detergents or cleaning agents are used today, for example by mixing and / or granulating additives and / or raw materials produced, with certain proportions of additives and raw materials also liquid, for example can be present as an aqueous solution or aqueous dispersion.
  • the solid additives can by spray drying, granulation, roller compaction, extrusion or other compaction measures have been produced.
  • liquid organic substances for example nonionic surfactants, or aqueous Solutions or aqueous dispersions have been used.
  • surfactants especially anionic surfactants, are known to be both in aqueous form (as a paste) as well as in solid form (as a powder or additive).
  • anionic surfactants Alkyl benzene sulfonates and alkyl sulfates.
  • Alkylbenzenesulfonates in particular are important Anionic surfactants with excellent washing performance, but which have the disadvantage that they have very sticky properties, so that additives or detergents or cleaning agents with relatively high concentrations of alkylbenzenesulfonates, for example additives with Held above 30 wt .-% alkylbenzenesulfonates, tend to stick and thus the Free flowing properties of the agents impair as well as when redissolving in aqueous liquor - especially if the agents also have ethoxylated nonionic surfactants - for Tend to gel.
  • Inorganic builder substances like zeolite A, which has been the preferred one in recent years inorganic builders in detergents or cleaning agents are either considered (spray dried) powder, aqueous stabilized dispersion or as part of a solid, mostly granular additives incorporated into the washing or cleaning agents.
  • Prefers are solid additives for the production of which aqueous dispersions have been used in particular were spray dried. Such spray-dried additives often contain additives Anionic surfactants, for example alkylbenzenesulfonates, and other non-temperature and Ingredients sensitive to spray drying, especially those which are also preferred in aqueous form can be used.
  • Zeolite A has in the The past as an excellent carrier for those who tend to stick Alkylbenzenesulfonates, but also for the others mostly used in aqueous form Components or liquid at room temperature to slightly elevated temperatures
  • Constituents of washing or cleaning agents for example nonionic surfactants, textile-softening cationic surfactants or foam inhibitors such as silicone oils and paraffin oils, proven.
  • Newer inorganic builders such as zeolite P, layered crystalline disilicate or amorphous Silicates with delayed disintegration, however, are only limited by spray drying ready for use and are usually available as raw materials or separate, dry compounds posed.
  • Spray drying processes are unfavorable manufacturing processes from an energetic point of view for detergents or cleaning agents. There has been no shortage of attempts Provide processes for the production of detergents or cleaning agents based on spray drying either entirely or at least to spray drying base granules can do without.
  • zeolite A in amounts less than 10% by weight (based on the anhydrous active substance), and also have no alkylbenzenesulfonate as the anionic surfactant, and in particular no spray-dried granules containing zeolite A and optionally Alkylbenzenesulfonate and the usual others, mostly used in aqueous form Containing constituents, the problem arises, like the others mostly in aqueous Form used further ingredients of detergents or cleaning agents in the agent can be incorporated.
  • the invention accordingly relates to an additive in a first embodiment for use in detergents or cleaning agents, which organic builder substances and at least 1 further ingredient selected from sequestrants and optical Brighteners and, if necessary, other ingredients of washing or cleaning agents contains, whereby alkylbenzenesulfonates are excluded and the content of the additives Zeolite A should not be more than 10% by weight, based on anhydrous active substance.
  • the invention also relates to a washing or cleaning agent which comprises the inventive Additives and in particular the additives produced according to the invention contains, but is free of alkylbenzenesulfonates and zeolite A not in amounts above 10 % By weight, based on anhydrous active substance.
  • the invention is based on the idea of as many as possible, and preferably all, of the components a washing or cleaning agent, which so-called small components such Represent cobuilders, optical brighteners, sequestering agents, graying inhibitors, soap, etc. and in particular those which are usually used in aqueous form, in one Unite additive.
  • small components such Represent cobuilders, optical brighteners, sequestering agents, graying inhibitors, soap, etc. and in particular those which are usually used in aqueous form, in one Unite additive.
  • This has the advantage that only a small part instead of the Most of the detergent or cleaning agent is spray dried or on another Way must be dried.
  • this additive enables homogeneous distribution of these small components.
  • the additives according to the invention have above all organic builder substances, which are usually used as cobuilders, preferably (co) polymers Polycarboxylates.
  • copolymeric polycarboxylates also counted those polymers which are made up of more than 2 monomers are.
  • the content of the organic builder substances in the additives according to the invention can vary widely. In principle, it could amount to Make up 2 to 98 wt .-%.
  • preferred additives contain 20 to 80% by weight and in particular 30 to 70% by weight of organic builder substances, contents of 40 to 60 % By weight of (co) polymeric polycarboxylates are particularly advantageous.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided such use is not objectionable for ecological reasons, as well as mixtures from these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures from these.
  • the acids themselves can also be used.
  • the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of detergents or cleaning agents.
  • citric acid succinic acid, glutaric acid, adipic acid, To name gluconic acid and any mixtures of these.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
  • a preferred dextrin is described in British patent application 94 19 091.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-93/16110, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A- 95/20608 known.
  • Oxidized oligosaccharides according to DE-A-196 00 018 are also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
  • Polyaspartic acids are particularly preferred or their salts and derivatives, of which in the German patent application P 195 40 086.0 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.
  • polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example as in European patent application EP-A-0 280 223 described, can be obtained.
  • Preferred polyacetals are made from dialdehydes such as Glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • ethylenediamine disuccinate preferably ethylenediamine disuccinate.
  • glycerol disuccinates and glycerol trisuccinates such as those found in the United States Patents US 4,524,009, US 4,639,325, in the European patent application EP-A-0 150 930 and Japanese patent application JP 93/339896 will.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
  • Such cobuilders are used, for example, in the international Patent application WO-A-95/20029.
  • Suitable polymeric polycarboxylates are, for example, sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular weight, based on free acids is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000.
  • Die (Co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution are used, in the context of this invention 20 to 55 wt .-% aqueous solutions are preferred.
  • Such (co) polymeric polycarboxylates are particularly preferred in the context of this invention.
  • This includes polymers from more than two different monomer units, for example, those according to DE-A-43 00 772 as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
  • copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • the known sequestering agents are mainly the salts of polyphosphonic acids and in particular the neutral sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate (HEDP), diethylene triamine penta methylene phosphonate and / or ethylenediaminetetramethylenephosphonate is preferred.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • NTA nitrilotriacetic acid and / or their salts
  • NTA ethylenediaminetetraacetic acid
  • EDTA ethylenediaminetetraacetic acid
  • the content of the additives according to the invention in one or more of these sequestering agents is preferably 2 to 8% by weight and in particular 3 to 6% by weight. As special Values between 4 and 5% by weight have proven to be advantageous.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or their Contain alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar connections, which instead of the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Can continue Present brighteners of the substituted diphenylstyryl type, e.g.
  • Phthalocyanines and their salts are among the optical brighteners. Mixtures of the aforementioned brighteners can be used
  • the content of the additives according to the invention in one or more optical brighteners is preferably at least 1.5% by weight in total and in particular 2 to 5% by weight.
  • dyes can also be incorporated into the additives.
  • additives can - if they are used as an additive component in detergents or cleaning agents serve - for example, serve as colored speckles.
  • the so-called small components in washing or cleaning agents generally include also soaps normally used in the finished products in quantities of less than 5 wt .-% are included.
  • the additives according to the invention can therefore also be soaps, in particular saturated fatty acid soaps, but optionally also in combination with unsaturated Fatty acid soaps.
  • the sodium and / or potassium salts are particularly suitable of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures.
  • the known alkenyl succinic acid salts can also be used as a substitute for soaps will.
  • the content of the additives in soaps and / or alkenyl succinic acid salts is 5 to 10% by weight in a preferred embodiment of the invention, but can well below and above.
  • Non-ionic surfactants which are liquid at room temperature are not directly counted as small components, even if they are only present in amounts of about 2 to 3% by weight in some finished compositions. Even in these small quantities, the nonionic surfactants, in particular in combination with anionic surfactants, make a significant contribution to the washing performance and are usually included in one of the main components - generally the surfactants.
  • nonionic liquid surfactants are rarely used in aqueous solution or dispersion - exceptions are, for example, pastes made from anionic surfactants and nonionic surfactants - their incorporation into detergents or cleaning agents can still cause problems regarding the free-flowing properties of the product or because of it Tendency to gel when the product is redissolved in an aqueous liquor.
  • Nonionic surfactants which are liquid at room temperature or only slightly elevated temperature if appropriate also in combination with nonionic surfactants which are solid at these temperatures, are therefore further preferred ingredients of the additives according to the invention.
  • ethoxylated and / or propoxylated alcohols such as fatty alcohols, oxo alcohols or petrochemical-based alcohols with a similar (but odd) carbon chain distribution as the fatty alcohols.
  • fatty alcohols such as fatty alcohols, oxo alcohols or petrochemical-based alcohols with a similar (but odd) carbon chain distribution as the fatty alcohols.
  • EO ethylene oxide
  • the alcohol radical can be methyl-branched linearly or preferably in the 2-position, or linear and methyl-branched radicals in a mixture can contain, as they are usually present in oxo alcohol residues.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants can also be used be contained in the additives, for example ethoxylated fatty acid methyl esters, alkyl glycosides, Polyhydroxy fatty acid amides (glucamides) or amine oxides (detailed description other non-ionic surfactants: see below). Your salary in the invention However, additives are less preferred.
  • the content of nonionic surfactants in the additives according to the invention is preferably 2 to 15% by weight and in particular 5 to 10% by weight.
  • the content of the additives at Room temperature or liquid nonionic surfactants at only a moderately elevated temperature depends on the type and amount of solid support material, since the invention Additives retain their free-flowing properties and should not stick together even during storage.
  • anionic surfactants usually belong not to the so-called small components. But if they are not in solid powder or granular to compounded form, but as an aqueous paste, if necessary in a mixture with nonionic surfactants, in the manufacture of washing or Cleaning agents are to be used, it may be advantageous if these are aqueous Anionic surfactants are introduced into the additive according to the invention. According to the invention but alkylbenzenesulfonates are excluded as ingredients of the additives. A more precise one A description of the anionic surfactants that may be used is given below.
  • the salary the additives according to the invention on anionic surfactants not containing alkylbenzenesulfonate is preferably 0.5 to 10% by weight, in particular 1 to 5% by weight.
  • solid fillers and carrier salts Components of the additives.
  • inorganic ones are suitable for this Builder substances such as crystalline layered silicates, in particular disilicates like SKS 6®, Zeolite P like Zeolite MAP® or silicates with delayed disintegration (see below for a more detailed description).
  • the content of zeolite A preferably less than 10% by weight and in particular 0 to 5 % By weight.
  • Suitable solid carriers are, however, inorganic salts such as, for example Sodium and / or potassium salts of carbonates, bicarbonates, sesquicarbonates, sulfates, Bisulfates and conventional water glasses, which are at least partially in aqueous form in the Processes for producing the additives can be introduced.
  • the invention makes these inorganic carrier salts less than 50 wt .-%, preferably less than 40% by weight of the additives according to the invention.
  • graying inhibitors which do the job have to keep the dirt detached from the fiber suspended in the liquor and so to prevent the dirt from re-opening.
  • water-soluble colloids are used mostly of an organic nature, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or the cellulose or salts of acidic sulfuric acid esters of cellulose or Strength.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose suitable.
  • Soluble starch preparations and others other than those mentioned above can also be used Use starch products, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinyl pyrrolidone is useful.
  • cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the funds used.
  • the additives according to the invention differ depending on the type of their production Bulk weights between about 250 to about 900 g / l, but bulk weights above of 400 g / l and in particular above 500 g / l are particularly preferred.
  • the additives (after drying) have less than 10% by weight and preferably less than 5% by weight of free water. Especially it is even preferred that the total amount of water, ie the sum of chemical and / or physically bound and unbound, i.e. free water even makes up less than 10% by weight and in particular even less than 5% by weight.
  • the Additives have typical granular structures, although they are optional - for example, if they are to be used as additives to almost spherical particles - rounded can be.
  • Advantageous embodiments of the invention also provide that the additives - apart from of water and residual components / salts, which from the solutions used in the Additives were introduced - at least 90% by weight from no more than 7 different ones Ingredients, preferably at least 92% by weight of not more than 5 different components.
  • 2 different optical Brighteners which are dosed separately in conventional processes, as 2 different ones Viewed components.
  • a preferred additive contains organic, preferably (co) polymeric cobuilders, 1 to 3 optical brighteners, non-ionic surfactant and / or soap, 1 to 2 different phosphonates and 1 to 2 solids as filler salts and carriers, preferably carbonate, bicarbonate, Sulfate, bisulfate or mixtures thereof.
  • a particularly preferred additive contains (co) polymeric polycarboxylates, non-ionic Surfactant and / or soap, 1 to 3 components selected from optical brighteners and phosphonates and sodium and / or potassium carbonate, the sum of the contents of (co) polymeric polycarboxylate and the carbonate make up between 70 and 85% by weight.
  • the usual fine-particle surface modifiers known from the prior art can be used here such as zeolite A, X and / or P, silicas and silicic acid derivatives, calcium stearate etc. and mixtures of these are used.
  • the amount of the optional The surface modifier used in zeolite A is the maximum that can be used in the additive The amount of zeolite A already included.
  • the additives can be made by any of the known methods such as spray drying, granulation with water as granulation aid and drying as well as compacting and Make drying. If necessary, aftertreatment can then be carried out with other treatments Ingredients in solid and / or liquid form. What manufacturing process is chosen depends on the amount of water used by those in aqueous form Raw materials and possibly compounds is provided. So offers at Amounts of water above 30% by weight, based on the mixture to be dried, on each Do the spray drying. With water contents up to 10 wt .-% is also generally granulation possible without difficulty. With water contents between 10 and 30 wt .-%, it is left to the skilled person, the most effective method to select for the manufacture of the additives.
  • (co) polymeric polycarboxylates are commercially available in aqueous form.
  • organic builders can be citric acid and citrate as an aqueous solution be used.
  • Acid and salt of citric acid can also be used as a solid be added.
  • organic builder substances as well as dye solutions, but optionally also solutions of the sequestering agents, the optical brighteners and Graying inhibitors and discoloration inhibitors, for example polyvinylpyrrolidone, optionally also water glass solutions, fatty acids and non-ionic surfactants, especially at room temperature or up to 30 ° C liquid nonionic surfactants Fat or oxo alcohol ethoxylates (for a more detailed description see below) represent the liquid ones Forms of preparation for the production of the additives according to the invention. Out For economic reasons, the highest possible with the aqueous preparation forms concentrated solutions or dispersions are used.
  • citric acid serves as solid components or citrate, alkali metal soaps and the other possible inorganic fillers and Carrier salts, especially sodium carbonate and / or sodium sulfate.
  • the solid and liquid components are mixed together, using it in principle It is irrelevant whether all liquid components are initially introduced and the solids mixed into them whether all solids are initially charged and the liquid components mixed or whether there is any order of addition. Out For reasons of process economy, however, the solids are preferred first submitted and then mixed in the liquids. Drying is done either by spray drying a slurry or in a conventional drying device after a performed granulation or compacting, the use of Fluid bed dryers is preferred. If desired - see above - can follow the drying still a surface modification according to the known methods of State of the art. The surface can be finely divided in a known manner Powders are coated.
  • the Additives according to the invention in particular the spray-dried additives as carriers for other liquids, in particular for nonionic surfactants, cationic surfactants and / or liquid to wax-like foam inhibitors based on silicone or paraffin in one subsequent granulation or compacting step.
  • the invention further relates to a powdery to granular washing or cleaning agent -
  • a powdery to granular washing or cleaning agent - which contains the additive according to the invention but is free from alkylbenzenesulfonates and zeolite A not in amounts above 10% by weight, based on anhydrous active substance.
  • the agents zeolite A only in amounts up to 8 wt .-%, advantageously contain up to 5% by weight and in particular 1 to 3% by weight even zeolite are A-free.
  • Additive contains all components necessary for the production of the finished agent in aqueous form are used, a detergent or cleaning agent containing such an additive, which contains all raw materials or compounds used in aqueous form, another preferred embodiment.
  • the detergents or cleaning agents can be any of the known methods are prepared, the spray drying from the given Problem should be essentially excluded.
  • Preferred manufacturing process are conventional granulations, compactings and extrusions, whereby the additives according to the invention either subsequently as a separate component be mixed with the agent or a feed component in the selected manufacturing process represent.
  • the additives according to the invention as an insert component in an extrusion process - advantageously in an extrusion process according to the teaching of European patent 0 486 592 B1 or the older one German patent application P 196 38 599.7 - are used.
  • washing or cleaning agents have the following ingredients, the invention is not limited to the ingredients mentioned.
  • anionic surfactants are those of the sulfonate type (to the exclusion of alkylbenzenesulfonates) and sulfates.
  • Suitable surfactants of the sulfonate type include, for example, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the Receives sulfonation products.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and Triester and their mixtures represent how they are produced by esterification by a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides can be obtained with 0.3 to 2 mol of glycerol.
  • the sulfonation products are a complex mixture represents the mono-, di- and triglyceride sulfonates with ⁇ -and / or internal Contains sulfonic acid grouping.
  • sulfonated fatty acid salts are formed, Glyceride sulfates, glycerine sulfates, glycerin and soaps. If you go from the saturated of saturated Fatty acids or hardened fatty acid glycerol ester mixtures, so the Percentage of ⁇ -sulfonated fatty acid disalts, depending on the procedure, up to about 60 % By weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates, as well as C 14 -C 15 alkyl sulfates and C 14 -C 16 alkyl sulfates are particularly preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as a commercial product from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • the soaps already mentioned can be considered as further anionic surfactants. she if they are not completely incorporated into the agents via the additive according to the invention are preferably mixed in subsequently.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of anionic surfactants in the washing or cleaning agents according to the invention is preferably 10 to 45% by weight in total, with it being preferred that Alk (en) yl sulfates or 2,3-alkyl sulfates are contained in amounts of 10 to 40% by weight.
  • the preferred anionic surfactants are alk (en) yl sulfates and / or 2,3-alkyl sulfates, which From an application point of view, alkylbenzenesulfonates in the washing or Can replace cleaning agents without sacrificing performance.
  • ingredients of the invention are primarily alkyl glycosides, polyhydroxy fatty acid amides and especially here the glucamides, ethoxylated fatty acid methyl esters and to name amine oxides.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • 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 described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than that Half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 represents a linear, branched or cyclic alkyl radical or an
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually identified by a so-called Spacer separated from each other. This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants means not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to international patent application WO-A-96/23768.
  • End group capped dimeric and trimeric mixed ethers according to the German Patent application DE-A-195 13 391 are particularly characterized by their bi- and Multifunctionality.
  • the end group-closed surfactants mentioned have good ones Network properties and are low-foaming, so that they are particularly suitable for use suitable in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955 can be described.
  • Zeolite P is crystalline as builder substances layered (di) silicates and amorphous silicates with delayed disintegration into consideration.
  • Zeolite A is used - if at all - only in the amounts already mentioned above.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” also means “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident when a textile is soiled that has already been washed several times with an inventive one Detergent containing this oil and fat-dissolving component has been washed.
  • non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, each based on the nonionic cellulose ether
  • polymers of phthalic acid and / or terephthalic acid or their Derivatives in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these.
  • sulfonated derivatives of phthalic acid and Terephthalic acid polymers are particularly preference is given to the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • bleaching agents that serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
  • Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used.
  • Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups.
  • acylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE-A-196 16
  • the bleach activator can be coated with coating substances in a known manner or, if necessary using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, granulated or extruded / pelletized and, if desired, others Additives, such as dye, contain. Such granules preferably contain over 70% by weight, in particular from 90 to 99% by weight, of bleach activator. Preferably a bleach activator is used which forms peracetic acid under washing conditions.
  • the transition metal compounds in question include in particular those known from the German patent application DE-A-195 29 905 manganese, iron, cobalt, Ruthenium or molybdenum salt complexes and those from the German patent application DE-A-196 20 267 known N-analog compounds, which from the German Patent application DE-A-195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum-carbonyl complexes, which are described in German patent application DE-A-196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogenous tripod ligands resulting from the German patent application DE-A-196 20 411 known cobalt, iron, copper and ruthenium amine complexes, the manganese described in German patent application DE-A-44 16 438, Copper and cobalt complexes described in European patent application EP-A-0 272 030 described cobalt complexes, which from the
  • Combinations of bleach activators and Transition metal bleaching catalysts are, for example, from the German patent application DE 196 13 103 and the international patent application WO-A-95/27775 known.
  • Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are in customary amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total Means used.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular, however, mixtures or mixtures containing protease and / or lipase with lipolytic enzymes of particular interest.
  • lipolytic acting enzymes are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which also Cellobiases are called, or mixtures of these are used. Because the different Distinguish cellulase types by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases will.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • a granulate 1 was produced by spray drying and subsequent post-treatment, which contained the following composition: 51.40% by weight of copolymeric sodium salt of acrylic acid and maleic acid (Sokalan CP 5®, commercial product from BASF, Federal Republic of Germany; used as 40% by weight % aqueous solution), 7.02% by weight of tallow fatty alcohol with 5 EO, 8.16% by weight of C 12 -C 18 sodium fatty acid soap, 27.14% by weight of sodium carbonate (used as a solid), 2.01 % By weight bis ((4-anilino-6-morpholino-s-triazin-2-yl) amino) -stilbene-2,2'-disulfonic acid disodium salt (used as an aqueous suspension), 2.77% by weight other salts and water and 1.50% by weight of C 12 -C 18 fatty alcohol with 7 EO, which was subsequently sprayed on.
  • This granulate 1 had a bulk density of 250 g / l.
  • the granulate 3 was obtained by granulation and subsequent drying of an aqueous Solution of Sokalan CP 5®, liquid at room temperature or slightly elevated temperature non-ionic surfactants, fatty acid soap (see above), sodium carbonate and 2 different optical brighteners bis ((4-anilino-6-morpholino-s-triazin-2-yl) amino) -stilbene-2,2'-disulfonic acid disodium salt and bis (2-sulfostyrene) biphenyl disodium salt.
  • the salary polymer after drying was 49.1% by weight, sodium carbonate 27.4% by weight optical brighteners 2.88% by weight, 7.80% by weight of soap and nonionic surfactants 8.50% by weight.
  • the rest consisted of water and other salts.
  • the bulk density of Granulate 3 was 580 g / l.
  • Granulate 3 was suitable as a separate subsequent admixture component in heavy Detergents or cleaning agents with bulk weights between 500 and 900 g / l.
  • the granules 1 to 3 were also suitable as fixed components in granulation or compacting processes for the production of heavy detergents or cleaning agents.

Landscapes

  • 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)
  • Detergent Compositions (AREA)
EP97121101A 1996-12-09 1997-12-01 Additif détergent Expired - Lifetime EP0846758B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19651072A DE19651072A1 (de) 1996-12-09 1996-12-09 Additiv für Wasch- oder Reinigungsmittel
DE19651072 1996-12-09

Publications (3)

Publication Number Publication Date
EP0846758A2 true EP0846758A2 (fr) 1998-06-10
EP0846758A3 EP0846758A3 (fr) 1998-12-16
EP0846758B1 EP0846758B1 (fr) 2006-03-01

Family

ID=7814096

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97121101A Expired - Lifetime EP0846758B1 (fr) 1996-12-09 1997-12-01 Additif détergent

Country Status (4)

Country Link
EP (1) EP0846758B1 (fr)
AT (1) ATE318887T1 (fr)
DE (2) DE19651072A1 (fr)
ES (1) ES2258785T3 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000020550A1 (fr) * 1998-10-05 2000-04-13 The Procter & Gamble Company Procede d'apport d'agglomerat chelateur a une composition de detergent afin d'ameliorer sa stabilite au stockage, son aptitude a la fluidification et la facilite avec laquelle on peut prelever des doses d'utilisation
US6635612B1 (en) 1999-10-01 2003-10-21 The Procter & Gamble Company Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability
EP1500696A1 (fr) * 2003-07-25 2005-01-26 Clariant GmbH Détergent additif

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19858859A1 (de) 1998-12-19 2000-06-21 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Granulate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2442423A1 (de) * 1973-09-14 1975-04-03 Ciba Geigy Ag Staubfreie, gut rieselfaehige granulate von optischen aufhellern
DE3604223A1 (de) * 1985-02-14 1986-08-14 Basf Ag, 67063 Ludwigshafen Zusaetze fuer wasch- und reinigungsmittel
EP0385562A2 (fr) * 1989-01-03 1990-09-05 Amway Corporation Détergent pour le linge
WO1992013937A1 (fr) * 1991-02-11 1992-08-20 Henkel Kommanditgesellschaft Auf Aktien Additif granule pour produits de lavage et de nettoyage
DE4213036A1 (de) * 1992-04-21 1993-10-28 Henkel Kgaa Granulares, alkalisches, phosphatfreies Reinigungsadditiv
WO1997029175A1 (fr) * 1996-02-12 1997-08-14 Unilever N.V. Composition detergente contenant de l'acide nitrilotriacetiq ue (nta) et/ou de l'acide ethylenedinitrilotetracetique (edta)

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2442423A1 (de) * 1973-09-14 1975-04-03 Ciba Geigy Ag Staubfreie, gut rieselfaehige granulate von optischen aufhellern
DE3604223A1 (de) * 1985-02-14 1986-08-14 Basf Ag, 67063 Ludwigshafen Zusaetze fuer wasch- und reinigungsmittel
EP0385562A2 (fr) * 1989-01-03 1990-09-05 Amway Corporation Détergent pour le linge
WO1992013937A1 (fr) * 1991-02-11 1992-08-20 Henkel Kommanditgesellschaft Auf Aktien Additif granule pour produits de lavage et de nettoyage
DE4213036A1 (de) * 1992-04-21 1993-10-28 Henkel Kgaa Granulares, alkalisches, phosphatfreies Reinigungsadditiv
WO1997029175A1 (fr) * 1996-02-12 1997-08-14 Unilever N.V. Composition detergente contenant de l'acide nitrilotriacetiq ue (nta) et/ou de l'acide ethylenedinitrilotetracetique (edta)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SMULDERS E.: 'LAUNDRY DETERGENTS', WILEY *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000020550A1 (fr) * 1998-10-05 2000-04-13 The Procter & Gamble Company Procede d'apport d'agglomerat chelateur a une composition de detergent afin d'ameliorer sa stabilite au stockage, son aptitude a la fluidification et la facilite avec laquelle on peut prelever des doses d'utilisation
US6635612B1 (en) 1999-10-01 2003-10-21 The Procter & Gamble Company Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability
EP1500696A1 (fr) * 2003-07-25 2005-01-26 Clariant GmbH Détergent additif

Also Published As

Publication number Publication date
ATE318887T1 (de) 2006-03-15
EP0846758A3 (fr) 1998-12-16
DE19651072A1 (de) 1998-06-10
DE59712584D1 (de) 2006-04-27
ES2258785T3 (es) 2006-09-01
EP0846758B1 (fr) 2006-03-01

Similar Documents

Publication Publication Date Title
EP0863200A2 (fr) Compositions détergentes sous forme de tablettes
EP0804529B1 (fr) Compose silicate alcalin amorphe
EP1842900A1 (fr) Procédé destiné à la fabrication de granulés et leur utilisation dans des agents de lavage et/ou de nettoyage
EP0828818B1 (fr) Produit de lavage ou detergent en granules a densite en vrac elevee
EP0986629B1 (fr) Detergent granule
EP0846758B1 (fr) Additif détergent
EP0840780B1 (fr) Produit granule de lavage ou de nettoyage a masse volumique apparente elevee
EP0853117B1 (fr) Détergent granulaire pour une meilleure élimination des salissures grasses
EP0845028B1 (fr) Procede de production d'un silicate alcalin amorphe soumis a une impregnation
EP0888450B2 (fr) Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe
EP0888428A1 (fr) Procede de production de silicates granulaires a masse volumique apparente elevee
DE19936614B4 (de) Verfahren zur Herstellung eines Waschmittels
WO2000022076A1 (fr) Granules renfermant du phosphonate
EP0919614B1 (fr) Procédé de production des compositions détergentes à haute densité
EP0986627A1 (fr) Agents de lavage ou de nettoyage a pouvoir nettoyant eleve
WO1997034991A1 (fr) Procede de production de detergents ou de nettoyants granulaires coulants
DE19700775A1 (de) Verfahren zur Herstellung aniontensidhaltiger wasch- und reinigungsaktiver Tensidgranulate
DE19936612A1 (de) Niederdosierter, löslicher Builder
DE102004053385A1 (de) Kugelförmige Agglomerate
DE19911570A1 (de) Aniontensid-Granulate
WO1998001532A2 (fr) Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe
DE19632284A1 (de) Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung
WO2016142209A1 (fr) Détergent ou produit de nettoyage granulaire à solubilité améliorée
EP1004658A2 (fr) Agent de lavage comprenant de l'acide citrique
DE19846439A1 (de) Waschmittel mit kationischen Alkyl- und/oder Alkenylpolyglykosiden

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19971201

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE DE ES FR IT NL

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

AKX Designation fees paid

Free format text: AT BE DE ES FR IT NL

17Q First examination report despatched

Effective date: 20020419

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

GRAL Information related to payment of fee for publishing/printing deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR3

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060301

REF Corresponds to:

Ref document number: 59712584

Country of ref document: DE

Date of ref document: 20060427

Kind code of ref document: P

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2258785

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061231

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20061204

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 20061231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061201

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 19

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20161213

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20161213

Year of fee payment: 20

Ref country code: FR

Payment date: 20161222

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20161223

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59712584

Country of ref document: DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20180508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20171202