EP0846758B1 - Additif détergent - Google Patents

Additif détergent Download PDF

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Publication number
EP0846758B1
EP0846758B1 EP97121101A EP97121101A EP0846758B1 EP 0846758 B1 EP0846758 B1 EP 0846758B1 EP 97121101 A EP97121101 A EP 97121101A EP 97121101 A EP97121101 A EP 97121101A EP 0846758 B1 EP0846758 B1 EP 0846758B1
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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.)
Expired - Lifetime
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EP97121101A
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German (de)
English (en)
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EP0846758A3 (fr
EP0846758A2 (fr
Inventor
Rene-Andres Dr. Artiga Gonzalez
Volker Dr. Bauer
Monika Dr. Böcker
Fred Dr. Schambil
Heinke Jebens
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP0846758A2 publication Critical patent/EP0846758A2/fr
Publication of EP0846758A3 publication Critical patent/EP0846758A3/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
    • 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 cleaners, a process for its preparation and detergents or cleaners containing these additives.
  • Modern powder-form or granular detergents or cleaners are produced today, for example, by mixing and / or granulating additives and / or raw materials, certain proportions of the additives and raw materials also being liquid, for example as an aqueous solution or aqueous dispersion.
  • the solid additives can be obtained by spray drying. Granulation, roll compaction, extrusion or other compaction measures have been prepared. Also in the preparation of the additives, it is possible to use liquid organic substances, for example nonionic surfactants, or aqueous solutions or aqueous dispersions.
  • the essential constituents of detergents or cleaning agents include the surfactants.
  • Surfactants in particular anionic surfactants, are known to be usable both in aqueous form (as a paste) and in solid form (as a powder or additive).
  • anionic surfactants are alkylbenzenesulfonates and alkyl sulfates.
  • alkylbenzenesulfonates are important anionic surfactants with excellent washing performance, but which have the disadvantage that they have highly sticky properties, so that additives or detergents or cleaning agents with relatively high concentrations of alkylbenzenesulfonates, for example, additives having contents above 30 wt .-% alkylbenzenesulfonates , tend to stick and thus affect the flowability of the agents as well as the redissolution in aqueous liquor - especially if the agent additionally also have ethoxylated nonionic surfactants - tend to gelling.
  • detergents or cleaners are builders, which may be both inorganic and organic.
  • Inorganic builder substances such as zeolite A, which in recent years has been the preferred inorganic builder in detergents or cleaners, are incorporated into the detergents either as a (spray-dried) powder, aqueous stabilized dispersion or as a constituent of a solid, mostly granular additive
  • such spray-dried additives contain anionic surfactants, for example alkylbenzenesulfonates, and other non-temperature and spray-drying components, especially those which are likewise preferably used in aqueous form.
  • anionic surfactants for example alkylbenzenesulfonates
  • other non-temperature and spray-drying components especially those which are likewise preferably used in aqueous form.
  • These include, for example, (co) polymeric polycarboxylates (organic builders), optical brighteners or dyes.
  • Zeolite A has in the past as an excellent carrier for the particular liable for sticking alkylbenzenesulfonates, but also for the other components usually used in aqueous form or at room temperature to slightly elevated temperatures liquid components of detergents or cleaners, such as nonionic surfactants, fabric softening Cationic surfactants or foam inhibitors such as silicone oils and paraffin oils.
  • newer inorganic builders such as zeolite P, layered crystalline disilicates or amorphous silicates with delayed disintegration are only conditionally usable by the spray drying and are usually provided as raw materials or separate, dry compounds.
  • Spray drying processes are unfavorable manufacturing processes for detergents or cleaners from an energetic point of view. There has therefore been no lack of attempts to provide processes for the production of detergents or cleaning agents that can dispense with spray drying either completely or at least on the spray drying of basic granules.
  • zeolite A in amounts less than 10 wt .-% (based on the anhydrous active substance), and also no alkylbenzenesulfonate as an anionic surfactant and in particular do not contain spray-dried granules, soft Zeolite A and optionally alkylbenzenesulfonate and the usual, usually used in aqueous form further constituents, thus raises the problem how the other used mostly in aqueous form further ingredients of detergents or cleaning agents can be incorporated into the agent.
  • the present invention solves this problem
  • the invention accordingly relates to a first embodiment.
  • a process for the preparation of the additives according to the invention wherein at least a part of the organic builders and at least one further ingredient selected from sequestering agents and optical brighteners, presented in aqueous form, optionally mixed with solids and then dried.
  • at least 60% by weight, and in particular 70 to 100% by weight, of the total amount of organic builder substances present in aqueous form are initially introduced.
  • a post-treatment with ingredients of detergents or cleaners in solid and / or liquid Form be performed.
  • the invention likewise relates to a washing or cleaning agent which contains the additives according to the invention and in particular the additives according to the invention, but is free from alkylbenzenesulfonates and zeolite A not in amounts above 10% by weight. based on anhydrous active substance having.
  • the invention is based on the idea of as many, desirably all components of a detergent or cleaning agent, which are so-called small components such as cobuilders, optical brighteners, sequestering agents, grayness inhibitors, soap, etc. and in particular those which are usually used in aqueous form, in one Additive additive.
  • small components such as cobuilders, optical brighteners, sequestering agents, grayness inhibitors, soap, etc. and in particular those which are usually used in aqueous form
  • Additive additive This has the advantage that only a small part has to be spray-dried or dried in some other way instead of the main part of the washing or cleaning agent.
  • this additive it is possible by the use of this additive, the homogeneous distribution of these small components.
  • the additives according to the invention have, above all, organic builder substances which are usually used as co-builders, preferably (co) polymeric polycarboxylates.
  • copolymeric polycarboxylates also include those polymers which are made up of more than 2 monomers.
  • the content of the organic builders in the additives of the invention can vary widely.
  • the additives contain from 20 to 80% by weight and in particular from 30 to 70% by weight of organic builders, with contents of from 40 to 60% by weight of (co) polymeric polycarboxylates being particularly advantageous.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid. Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, and mixtures thereof.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acids and mixtures of these.
  • the acids can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or renaturants.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • 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, for example acid or enzyme-catalyzed processes. Preference is given to hydrolysis products having average molecular weights in the range from 400 to 500,000.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100.
  • DE dextrose equivalent
  • Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 are useful.
  • 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 aikohot function of the saccharide ring to the carboxylic acid functionality.
  • Such 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 and international patent applications WO-A A-92 / 18,542th WO-A-93/08251, WO-A-93/16110.
  • oxidized oligosaccharides according to DE-A-196 00 018.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives of which German patent application P 195 40 086.0 discloses that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in European Patent Application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • co-builders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • glycerol disuccinates and glycerol trisuccinates are particularly preferred in this context, as described, for example, in US Pat. Nos. 4,524,009 and 4,639,325, in US Pat European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such co-builders are described, for example, in International Patent Application WO-A-95/20029.
  • Suitable polymeric polycarboxylates are, for example, sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their molecular weight relative to free acids is generally from 5000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution to 55 wt .-% aqueous solutions are preferred.
  • Such (co) polymeric polycarboxylates are particularly preferred in the context of this invention. These also include polymers of more than two different monomer units, for example those which 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 monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • the salts of polyphosphonic acids and in particular the neutrally reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate (HEDP), diethylenetriaminepenta-methylenephosphonate and / or ethylenediamine tetramethylenephosphonate are preferred.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • diethylenetriaminepenta-methylenephosphonate and / or ethylenediamine tetramethylenephosphonate are preferred.
  • NTA nitrilotriacetic acid and / or its salts
  • NTA ethylenediaminetetraacetic acid and / or salts thereof
  • EDTA ethylenediaminetetraacetic acid and / or salts thereof
  • the content of the additives according to the invention in one or more of these sequestering agents is preferably from 2 to 8% by weight and in particular from 3 to 6% by weight. Values between 4 and 5% by weight have proven particularly advantageous.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisuffonklare or their 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 similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
  • the content of the additives according to the invention in one or more optical brighteners is in total from 2 to 5% by weight.
  • dyes can also be incorporated into the additives.
  • Such additives can then serve - if they serve as Zumischkomponente in detergents or cleaning agents - for example, as a colored speckles.
  • the so-called Kleinkomponeriten.in detergents or cleaners generally include soaps, which are normally included in the finished compositions in amounts of less than 5 wt .-%.
  • the additives according to the invention therefore also contain soaps, in particular saturated fatty acid soaps, but optionally also in combination with unsaturated fatty acid soaps.
  • Particularly suitable are the sodium and / or potassium salts 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 Alkonylbernsteinkland can be used.
  • the content of the additives in soaps and / or alkenylsuccinic acid salts in a preferred embodiment of the invention is from 5 to 10% by weight, but may well be below or above this.
  • Non-ionic surfactants which are liquid at room temperature are not counted directly to the small components, even if they are present in some finished compositions only in amounts of about 2 to 3 wt .-%. Even in these small amounts, the nonionic surfactants, especially in combination with anionic surfactants, significantly contribute to the washing performance and are usually one of the main components of surfactants in general.
  • nonionic liquid surfactants are not used in aqueous solution or dispersion at room temperature - Exceptions are, for example, pastes from anionic surfactants and nonionic surfactants - but their incorporation into the detergents or cleaners can lead to problems regarding the flowability of the product or due to their tendency to gel in the re-dissolution of the product in aqueous liquor.
  • Liquid 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, therefore represent 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 similar (but odd) C chain distribution as the fatty alcohols.
  • fatty alcohols such as oxo alcohols or petrochemical-based alcohols with similar (but odd) C chain distribution as the fatty alcohols.
  • propoxylated alcohols such as fatty alcohols, oxo alcohols or petrochemical-based alcohols with similar (but odd) C chain distribution as the fatty alcohols.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are 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 1s alcohols containing 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 means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants may also be present in the additives, for example ethoxylated fatty acid methyl esters, alkyl glycosides, polyhydroxy fatty acid amides (glucamides) or amine oxides (more detailed description of the other nonionic surfactants: see below).
  • ethoxylated fatty acid methyl esters alkyl glycosides
  • polyhydroxy fatty acid amides glucamides
  • amine oxides more detailed description of the other nonionic surfactants: see below.
  • their content in the additives according to the invention is less preferred.
  • the content of nonionic surfactants of the additives according to the invention is preferably from 2 to 15% by weight and in particular from 5 to 10% by weight.
  • the content of the additives at room temperature or at only moderately elevated temperature liquid nonionic surfactants depends on the type and amount of the solid support material, as well as the additives of the invention retain their flowability and should not stick even when stored.
  • Anionic surfactants are - with the exception of automatic dishwashing detergents - usually not to the so-called small components. However, if they are not to be used in solid powdery or granular to compounded form, but as an aqueous paste, optionally in admixture with nonionic surfactants, in the preparation of washing or cleaning agents, it may be advantageous if these aqueous anionic surfactants in the inventive additive can be introduced.
  • alkylbenzenesulfonates are excluded as ingredients of the additives. A more detailed description of the potentially usable anionic surfactants is given below.
  • the content of the additives according to the invention of non-alkylbenzenesulfonate-containing anionic surfactants is preferably 0.5 to 10% by weight, in particular 1 to 5% by weight.
  • solid fillers and carrier salts are also constituents of the additives.
  • inorganic builders such as crystalline layered silicates, in particular disilicates such as SKS 6®, zeolite P such as zeolite MAP® or silicates with delayed disintegration are suitable for this purpose (for a more detailed description see below).
  • zeolite A based on anhydrous active substance should preferably be less than 10% by weight and in particular 0 to 5% by weight.
  • suitable solid carriers are inorganic salts such as, for example, sodium and / or potassium salts of carbonates, bicarbonates, sesquicarbonates, sulfates, bisulfates and customary water glasses, which can be incorporated at least partially in aqueous form into the process for the preparation of the additives.
  • these inorganic carrier salts account for less than 50% by weight. preferably less than 40% by weight of the additives according to the invention.
  • graying inhibitors which have the task of keeping suspended from the fiber dirt suspended in the fleet and so prevent the re-raising of the dirt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc.
  • polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,
  • the additives according to the invention have different apparent weights depending on the manner of their preparation about 250 to about 900 g / l, but bulk densities above 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. In this case, it is particularly preferred that the total amount of water, ie the sum of chemically and / or physically bound and unbound, ie free water, is even less than 10% by weight and in particular even less than 5% by weight.
  • the additives have typical granular structures, and optionally they can be rounded - for example, when they are to be used as additives to almost spherical particles.
  • Advantageous embodiments of the invention also provide that the additives - apart from water and residual components / salts, which were introduced from the solutions used in the additives - at least 90 wt .-% of not more than 7 different components, preferably at least 92 Wt .-% consist of not more than 5 different components.
  • 2 different optical brighteners which are metered separately in conventional processes, are considered to be 2 different components.
  • a preferred additive contains organic, preferably (co-) polymeric cobuilders, 1 to 3 optical brighteners, nonionic 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 necessarily contains (co) polymeric polycarboxylates, nonionic surfactant and / or soap, 1 to 3 constituents selected from optical brighteners and phosphonates and sodium and / or potassium carbonate, the sum of the contents of (co) polymeric polycarboxylate and the carbonate between 70 and 85 wt.% Make up, and wherein mandatory optical brightener anwezand are.
  • a surface modification to improve the trickling behavior is generally not required but may be of interest for increasing the bulk density of the additives.
  • the usual finely divided, known from the prior art surface modifiers such as zeolite A, X and / or P, silicic acids and silicic acid derivatives, calcium stearate, etc., and mixtures thereof can be used.
  • the amount of optionally used surface modifier zeolite A is already included in the maximum amount of zeolite A that can be used in the additive.
  • the additives can be prepared by any of the known processes, such as spray drying, granulation with water as granulation aid and drying, and compaction and drying. Optionally, a subsequent treatment with further ingredients in solid and / or liquid form can then take place.
  • Which production method is chosen depends on the amount of water provided by the raw materials used in aqueous form and optionally compounds. Thus, at water amounts above 30 wt.%, Based on the mixture to be dried, in any case, the spray-drying. At water contents up to 10% by weight, granulation is generally possible without difficulty. At water contents of between 10 and 30% by weight, it remains within the skill of the art to select the most effective method of preparing the additives.
  • polymeric polycarboxylates are commercially available in aqueous form.
  • Citric acid and citrate can be used as aqueous solution as further organic builder substance.
  • acid and salt of citric acid can also be added as a solid.
  • These organic builders and dye solutions but optionally also solutions of sequestering agents, optical brighteners and graying inhibitors and discoloration inhibitors, for example polyvinylpyrrolidone, but optionally also waterglass solutions, fatty acids and nonionic surfactants, especially at room temperature or liquid to 30 ° C nonionic surfactants all fatty or oxo alcohol ethoxylates (see below for a more detailed description) represent the liquid preparation forms for the preparation of the additives according to the invention. For economic reasons, the most highly concentrated solutions or dispersions are used in the aqueous preparation forms.
  • the solid and liquid components are mixed together, and it is irrelevant in principle, whether initially presented all the liquid ingredients and the solids are mixed into it, whether submitted all solids and the liquid ingredients are added or if any order of addition is done.
  • the solids are preferably initially introduced, and then the liquids are admixed.
  • the drying is carried out either by spray-drying a slurries or in a conventional drying apparatus after a granulation or compaction has been carried out, wherein the use of fluidized-bed dryers is preferred. If desired - see above - may be carried out after the drying nor a microwavenrnodifzierung according to the known methods of the prior art.
  • the surface can be coated in a known manner with finely divided powders.
  • the additives according to the invention in particular the spray-dried additives, serve as carriers for further liquids, in particular for nonionic surfactants, cationic surfactants and / or liquid to waxy foam inhibitors based on silicone or paraffin in a subsequent granulation or compaction step.
  • the invention further relates to a powdered to granular detergent or cleaning agent - wherein in Also included in the scope of this invention are extruded detergents or cleaners to the granular detergents or cleaners, which contains the additive of the invention, but is free of alkylbenzenesulfonates and zeolite A not in amounts above 10 wt.%, Based on anhydrous active substance. It is particularly preferred that the agents contain zeolite A only in amounts of up to 8 wt.%, Advantageously, up to 5 wt .-% and in particular 1 to 3 wt .-% or even zeolite A-free.
  • the additive according to the invention contains all constituents which are used for producing the finished composition in aqueous form
  • a washing or cleaning agent which contains such an additive which contains all raw materials or compounds used in aqueous form constitutes another preferred embodiment.
  • the washing or cleaning agents can be prepared by any of the known methods, wherein the spray drying should be excluded from the given problem out substantially.
  • Preferred production processes are conventional granulations, compactions and extrusions, wherein the additives according to the invention are added to the agent either as a separate component or as an insert component in the selected preparation process.
  • the additives of the invention are used 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 earlier German Patent Application P 196 38 599.7.
  • the washing or cleaning agents may have the following ingredients, but the invention is not limited to the ingredients mentioned.
  • anionic surfactants for example, those of the sulfonate type (excluding alkylbenzenesulfonates) and sulfates are used.
  • surfactants of the sulfonate type are olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12 -C 18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis Sulfon réelles reside receives into consideration.
  • alkanesulfonates which are 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 esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.
  • the sulfonation products represent a complex mixture containing mono-, di- and triglyceride sulfonates with ⁇ -permanent and / or internal sulfonic acid moiety.
  • By-products are sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerine and soaps. Assuming in the case of the saturation of saturated fatty acids or hydrogenated fatty acid glycerol ester mixtures, the proportion of ⁇ -sulfonated fatty acid disalts may well be up to about 60% by weight, depending on the method used.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of Schwefelklareschester the C 12- C 18 fatty alcohols, for example, from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10 -C 20 oxo alcohols, and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates and C 14 -C 16 -alkyl sulfates are particularly preferred.
  • 2,3-Alkyl sulfates which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as a commercial product of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO are suitable. They are used in detergents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.
  • Suitable further anionic surfactants are the soaps already mentioned above. If they are not completely incorporated into the compositions via the additive according to the invention, they are preferably added subsequently.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present 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 detergents or cleaners according to the invention is preferably 10 to 45% by weight in total, it being preferred for alk (en) ylsulfates or 2.3-alkyl sulfates to be present in amounts of 10 to 40% by weight ,
  • the preferred anionic surfactants are alk (en) ylsulfates and / or 2,3-alkyl sulfates, which alkylbenzenesulfonates from an application point of view can replace in the detergents or cleaners according to the invention without any loss of performance.
  • alkyl glycosides may contain ingredients of the additives according to the invention, but also outside the additives in the detergents or cleaning agents, alkyl glycosides, polyhydroxy fatty acid amides and, in particular, the glucamides, ethoxylated fatty acid methyl esters and amine oxides should be mentioned at this point ,
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants 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 from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • Particularly preferred are C 12 -C 18 fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (1) in R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 5 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1 -C 4 alkyl or phenyl radicals being preferred
  • [Z] a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups , or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also obtained here preferably 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 be converted into the desired polyhydroxy fatty acid amides, for example according to the teaching of international patent application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer”. This spacer is usually a carbon chain that should be long enough so that the hydrophilic groups are spaced enough to act independently of each other. 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 is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to 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-capped dimeric and trimeric mixed ethers according to the German patent application DE-A-195 13 391 are distinguished, in particular, by their bi- and multimeric functionality.
  • the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955.
  • Suitable builder substances are, in particular, zeolite P, if appropriate also X, crystalline layered (di) silicates and amorphous silicates with delayed disintegration. Zeolite A is used - if at all - only in the amounts already mentioned above.
  • Such crystalline sheet 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 is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6th which are delay-delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • compositions may also contain components that positively affect oil and grease washability from fabrics. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxy-propylcellulose with a proportion of methoxyl groups of 15 to 30 wt.% And to hydroxypropoxyl groups of 1 to 15 wt .-%, each based to the nonionic cellulose ether, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives phthalic and terephthalic acid polymers.
  • compositions are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof; in particular, alkali metal carbonate and amorphous alkali metal silicate, above all sodium silicate with a molar ratio of Na 2 O: SiO 2 of from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof
  • alkali metal carbonate and amorphous alkali metal silicate above all sodium silicate with a molar ratio of Na 2 O: SiO 2 of from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the content of the bleaching agents is preferably from 5 to 25% by weight and in particular from 10 to 20% by weight, it being advantageous to use perborate monohydrate or percarbonate.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and the enol esters, acyl
  • the bleach activator may be coated in a known manner with encapsulants or, optionally with the use of adjuvants, in particular methylcelluloses and / or carboxymethylcelluloses, granulated or extruded / pelleted and, if desired, further additives, for example dye.
  • adjuvants in particular methylcelluloses and / or carboxymethylcelluloses
  • Such a granulate preferably contains more than 70% by weight, in particular from 90 to 99% by weight, of bleach activator.
  • a bleach activator is used which forms peracetic acid under washing conditions.
  • the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP-A-0 446 982 and EP-A-0 453 003 may also be present as so-called bleach catalysts.
  • Suitable transition metal compounds include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salt complexes known from German patent application DE-A-195 29 905 and their known from German patent application DE-A-196 20 267 N-analogues, the manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes known from the German patent application DE-A-195 36 082, the manganese, iron described in the German patent application DE-A-196 05 688 , Cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which are known from the German patent application DE-A-196 20 411 known cobalt, iron, copper and ruthenium Ammine complexes, the manganese, copper and cobalt complexes described in German patent application DE-A-44 16 438, the cobalt complexes described in European patent application EP-A-0 272 030,
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent 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 foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated keselic acid or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes.
  • foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamides are preferred.
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, lipases or lipolytic enzymes, amylases, cellulases or mixtures thereof. Oxireductases are also suitable.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, 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 aftertreatment, which contained the following composition: 51.40% by weight of copolymeric sodium salt of acrylic acid and of maleic acid (Sokalan CP 5®, commercial product of BASF, Federal Republic of Germany, used as 40% by weight.
  • Sokalan CP 5® commercial product of BASF, Federal Republic of Germany, used as 40% by weight.
  • aqueous solution 7.02% by weight tallow fatty alcohol with 5 EO, 8.16% by weight C 12 -C 18 sodium fatty acid soap, 27.14% by weight sodium carbonate (used as solid), 2.01% by weight .-% bis ((4-anilino-6-morpholino-s-triazin-2-yl) amino) -stilbene-2,2'-disulphonic acid disodium salt (used as aqueous suspension), 2.77% by weight of other Salts and water and 1.50 wt .-% C 12 -C 18 fatty alcohol with 7 EO, which was sprayed on later.
  • This granule 1 had a bulk density of 250 g / l.
  • granules 1 100 parts by weight of the granules 1 were sprayed in a further subsequent step with 4.60 parts by weight of a 40 wt .-% aqueous solution of 1-hydroxyethane-1,1-diphosphonate.
  • the resulting granules 2 had a bulk density of 410 g / l. Further drying or surface modification with finely divided solids were not required to improve the flowability, but increased the bulk density. If the phosphonate was incorporated as an aqueous solution into the slurry to be spray-dried, a granule 1 * was obtained which likewise had an increased bulk density of about 410 g / l.
  • Granule 3 was prepared by granulation and subsequent drying of an aqueous solution of Sokalan CP 5®, liquid nonionic surfactants at room temperature or slightly elevated temperature, 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 content of polymer after drying was 49.1% by weight, of sodium carbonate 27.4% by weight. 2.88% by weight of optical brighteners, 7.80% by weight of soap and 8.50% by weight of nonionic surfactants.
  • the rest was water and other salts.
  • the bulk density of granules 3 was 580 g / l.
  • Granulate 3 was suitable as a separate subsequent admixing component in heavy detergents or cleaners with bulk densities between 500 and 900 g / l.
  • the granules 1 to 3 were also suitable as a solid starting component in granulation or Kompaktierbacter for the production of heavy detergents or cleaning agents.
  • the granules 1 to 3 were suitable to be used in extrusion processes according to the teachings of the European patent 0 486 592 or the German patent application DE-A-196 38 599.

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Claims (16)

  1. Additif pour la mise en oeuvre dans des produits de lavage ou de nettoyage, caractérisé en ce qu'il contient
    - 20 à 80% en poids de substances builder organiques,
    - 2 à 5% en poids d'azurants optiques ainsi que
    - du savon et/ou des sels de l'acide alcénylsuccinique

    et éventuellement des ingrédients supplémentaires de produits de lavage ou de nettoyage, les alkylbenzène-sulfonates étant exclus, et la teneur des additifs en zéolite A n'étant pas supérieure à 10% en poids, par rapport à la substance active anhydre.
  2. Additif selon la revendication 1, caractérisé en ce qu'il contient 30 à 70% en poids de substance builder organique, et avec une préférence particulière de 40 à 60% en poids de polycarboxylates (co)polymères.
  3. Additif selon l'une quelconque des revendications 1 ou 2, caractérisé en ce qu'il contient 5 à 10% en poids de savon.
  4. Additif selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il contient 2 à 15% en poids, de préférence 5 à 10% en poids de tensio-actifs non ioniques.
  5. Additif selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la teneur en sels inorganiques, en particulier en carbonate de sodium et/ou de potassium, est inférieure à 50% en poids, de préférence inférieure à 40% en poids.
  6. Additif selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la quantité totale d'eau représente moins de 10% en poids, de préférence moins de 5% en poids.
  7. Additif selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'à l'exception d'eau et de composants résiduels/sels, lesquels ont été entraînés dans les additifs à partir des solutions mises en oeuvre, il est constitué à au moins 90% en poids de pas plus de 7 composants différents.
  8. Procédé de préparation d'un additif selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'au moins une partie des substances builder organiques et au moins un ingrédient supplémentaire choisi parmi les agents séquestrants et les azurants optiques, se présentent sous forme aqueuse, mélangés éventuellement avec des solides, sont séchés, puis éventuellement traités ultérieurement avec des ingrédients de produits de lavage ou de nettoyage, sous une forme liquide et/ou solide.
  9. Procédé selon la revendication 8, caractérisé en ce que l'additif est préparé à l'aide d'un séchage par pulvérisation.
  10. Procédé selon la revendication 8 ou 9, caractérisé en ce que les additifs séchés par pulvérisation sont mis en oeuvre en tant que véhicules pour des liquides supplémentaires, en particulier pour des tensio-actifs non ioniques, des tensio-actifs cationiques, et/ou des agents anti-mousse liquides jusqu'à cireux, à base de silicone ou de paraffine, dans une étape suivante de granulation ou de compactage.
  11. Produit de lavage ou de nettoyage, caractérisé en ce qu'il contient un additif selon l'une quelconque des revendications 1 à 7, mais en ce qu'il est exempt d'alkylbenzène-sulfonates et ne présente pas de zéolite A en des quantités supérieures à 10% en poids, par rapport à la substance active anhydre.
  12. Produit selon la revendication 11, caractérisé en ce qu'il contient de la zéolite A en des quantités allant jusqu'à 8% en poids, de préférence jusqu'à 5% en poids, et en particulier en ce qu'il est exempt de zéolite A ou contient de 1 à 3% en poids de zéolite A.
  13. Produit selon la revendication 11 ou 12, caractérisé en ce qu'il contient un additif qui contient toutes les matières premières ou compounds mis en oeuvre sous forme aqueuse dans le produit de lavage ou de nettoyage.
  14. Produit selon l'une quelconque des revendications 11 à 13, caractérisé en ce qu'il contient l'additif selon l'une quelconque des revendications 1 à 7, sous la forme de composant séparé et ajouté ultérieurement en mélangeant.
  15. Procédé de préparation d'un produit de lavage ou de nettoyage selon l'une quelconque des revendications 11 à 14, caractérisé en ce qu'un additif selon l'une quelconque des revendications 1 à 7 est mis en oeuvre en tant que composant séparé et ajouté ultérieurement en mélangeant.
  16. Procédé de préparation d'un produit de lavage ou de nettoyage selon l'une quelconque des revendications 11 à 14, caractérisé en ce qu'un additif selon l'une quelconque des revendications 1 à 7 est mis en oeuvre en tant que composant d'utilisation dans un procédé de granulation, un procédé de compactage, ou un procédé d'extrusion.
EP97121101A 1996-12-09 1997-12-01 Additif détergent Expired - Lifetime EP0846758B1 (fr)

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DE19651072A DE19651072A1 (de) 1996-12-09 1996-12-09 Additiv für Wasch- oder Reinigungsmittel
DE19651072 1996-12-09

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BR9914614A (pt) * 1998-10-05 2001-10-02 Procter & Gamble Processo para fornecimento de aglomerado quelante a uma composição detergente para melhorar sua estabilidade ao armazenamento, capacidade de fluidez e capacidade de coleta
DE19858859A1 (de) 1998-12-19 2000-06-21 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Granulate
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
DE10334045A1 (de) * 2003-07-25 2005-02-10 Clariant Gmbh Additive für Wasch- und Reinigungsmittel

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DE2442423A1 (de) * 1973-09-14 1975-04-03 Ciba Geigy Ag Staubfreie, gut rieselfaehige granulate von optischen aufhellern

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DE3604223A1 (de) * 1985-02-14 1986-08-14 Basf Ag, 67063 Ludwigshafen Zusaetze fuer wasch- und reinigungsmittel
AU4712189A (en) * 1989-01-03 1990-07-12 Amway Corporation Nonionic laundry detergent composition
DE4104085A1 (de) * 1991-02-11 1992-08-13 Henkel Kgaa Granulares additiv fuer wasch- und reinigungsmittel
DE4213036A1 (de) * 1992-04-21 1993-10-28 Henkel Kgaa Granulares, alkalisches, phosphatfreies Reinigungsadditiv
EP0880577A1 (fr) * 1996-02-12 1998-12-02 Unilever N.V. Composition detergente contenant de l'acide nitrilotriacetique (nta) et/ou de l'acide ethylenedinitrilotetracetique (edta)

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DE2442423A1 (de) * 1973-09-14 1975-04-03 Ciba Geigy Ag Staubfreie, gut rieselfaehige granulate von optischen aufhellern

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ES2258785T3 (es) 2006-09-01
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EP0846758A3 (fr) 1998-12-16
DE19651072A1 (de) 1998-06-10
EP0846758A2 (fr) 1998-06-10

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