EP1081219B1 - Détergents sous forme solide - Google Patents

Détergents sous forme solide Download PDF

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Publication number
EP1081219B1
EP1081219B1 EP00118328A EP00118328A EP1081219B1 EP 1081219 B1 EP1081219 B1 EP 1081219B1 EP 00118328 A EP00118328 A EP 00118328A EP 00118328 A EP00118328 A EP 00118328A EP 1081219 B1 EP1081219 B1 EP 1081219B1
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Prior art keywords
acid
detergents
weight
ether
sulfates
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EP00118328A
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German (de)
English (en)
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EP1081219A3 (fr
EP1081219A2 (fr
Inventor
Manfred Dr. Weuthen
Ditmar Kischkel
Rainer Dr. Eskuchen
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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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
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the invention is in the field of washing, rinsing and cleaning agents and relates to new ones coated anionic surfactants, a process for their preparation and the use of the substances for Manufacture of washing, rinsing and cleaning agents, especially in tablet form.
  • anionic surfactants such as sodium lauryl sulfate
  • granules of anionic surfactants have been obtained either by drying the corresponding aqueous solutions or pastes or by direct neutralization of the acidic precursors of the surfactant, that is to say generally the sulfonic acids or sulfuric acid semiesters.
  • the acidic precursors of the surfactant that is to say generally the sulfonic acids or sulfuric acid semiesters.
  • spray mixing processes and drying in the thin layer are suitable. These processes share the task of producing products with a high surfactant content in order to be able to add the surfactants in high concentrations to detergents, dishwashing detergents and cleaning agents.
  • the object of the present invention was therefore to provide new detergents in solid form to provide on the basis of anionic surfactants, which - both alone and in the solid Final formulation - have a lower tendency to stick and at the same time stand out through a improved solubility, especially in the dosing chamber of washing machines and in cold water, distinguished.
  • Another task has also been to make detergent tablets based on the detergents mentioned, which also have an improved solubility have or easier wash-in via the dosing chamber of washing machines and dishwashers have or where the proportion of disintegrants can be reduced with the same solubility.
  • the invention relates to detergents in solid form, which are characterized in that they are made of anionic surface-active compounds as the core and a layer enveloping them consist of water-soluble salts of mineral acids or water-soluble salts of organic carboxylic acids, with the proviso that the coating substances have a water solubility of at least 10 g / l at 20 ° C and the anionic surfactants in amounts of Contain 20 to 99 wt .-%.
  • anionic surfactants that form the core of the detergents are soaps, alkylbenzenesulfonates, Alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, Sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, Monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, Mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates,
  • anionic surfactants contain polyglycol ether chains, they can be a conventional, but preferably have a narrow homolog distribution. Preferably be Coated alkyl sulfates, alkyl benzene sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof.
  • the proportion of anionic surface-active compounds in the detergents can be 20 to 99, preferably 50 to 95 and in particular 85 to 90 wt .-%.
  • Preferred alkylbenzenesulfonates preferably follow the formula (I) R-Ph-SO 3 X (I) in which R stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph for a phenyl radical and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • R stands for a branched, but preferably linear alkyl radical having 10 to 18 carbon atoms
  • Ph for a phenyl radical
  • X for an alkali and / or alkaline earth metal
  • ammonium alkylammonium
  • alkanolammonium or glucammonium dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts
  • Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary and / or secondary alcohols, which preferably follow the formula (II) R 2 O-SO 3 Y (II) in which R 2 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and Y represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol as well as their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
  • Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.
  • these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-containing olefins using the shop process.
  • Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®. Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®.
  • oxo alcohols such as those obtained by the classic Enichema or Condea oxo process by adding carbon monoxide and hydrogen to olefins.
  • These alcohol mixtures are a mixture of strongly branched alcohols.
  • Such alcohol mixtures are commercially available under the trade name Lial®.
  • Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.
  • the detergents according to the invention contain the substances enveloping the surfactant standard on solid - preferably in total amounts from 1 to 80 wt .-%, preferably from 5 to 50 and in particular from 5 to 20% by weight.
  • These coating substances according to claim 1 are water-soluble compounds, which have a water solubility at 20 ° C. of at least 10 g / l, preferably at least 50 Have g / l and in particular 100 g / l, and advantageously more, for the overall recipe have useful properties, such as complexing hardness and Heavy metal ions or the inhibition of gel phase formation.
  • the coating with water-soluble envelopes are also made from the melt.
  • these substances are the salts of inorganic mineral acids.
  • these substances are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and silicic acid, the alkali metal sulfate, alkali borates and perborates, the various alkali metal silicates ("water glasses") and alkali metal phosphates to be mentioned in particular.
  • Typical examples are magnesium sulfate heptahydrate or borax.
  • the salts of organic carboxylic acids are also used. Typical examples are the alkali and / or alkaline earth metal salts, aluminum or zinc salts of monocarboxylic acids with 1 to 22 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid.
  • the use of sodium acetate is particularly preferred.
  • corresponding C 2 -C 6 dicarboxylic acids can also be used, so that the corresponding salts of succinic acid, maleic acid, fumaric acid, glutaric acid and adipic acid are suitable as suitable coating substances in the same way as above.
  • salts of hydroxy-functionalized polyvalent carboxylic acids can also be used, such as the above-mentioned salts of malic acid, tartaric acid and in particular citric acid.
  • alkali metal citrates is particularly preferred here.
  • the detergents according to the invention can be produced by processes that are already in production of detergents are known. Basically, the surfactant grain is first Drying and optionally granulating an appropriate aqueous solution or paste, which is then brought into contact with an aqueous solution or melt of the coating substance becomes. This is preferably done at higher temperatures, with the coating substance on the Grain precipitates and essentially includes it.
  • the production is generalized of the new detergents in such a way that first an aqueous solution or paste of the anionic surface-active compound dries and on the resulting grain from a aqueous solution or melt precipitates a coating substance, possibly during the water evaporated. It is of course immediately clear that the process is one-step or two-step can be carried out.
  • the dried powder which in turn is a conventional powder Market product can trade, then coat.
  • preferably continuous Processes are either the aqueous surfactant preparations or the dried surfactant powder used together with the coating agents.
  • the drying device into which the aqueous surfactant preparations are introduced, preferably sprayed can be any drying apparatus.
  • the drying is carried out as spray drying in a drying tower.
  • the surfactant solutions or pastes are exposed to a drying gas stream in a finely divided form in a known manner.
  • Anionic surfactant powders are obtained, which are then intimately mixed with the required amount of coating substances in the form of an aqueous solution in a second step.
  • Components for this process such as, for example, paddle mixers from Lödige or in particular spray mixers from Schugi, are advantageous, in which the surfactant powder is placed in the mixing chamber and the aqueous solutions of the coating materials are sprayed on. It is also possible to carry out the drying of the aqueous surfactant preparations and the mixing simultaneously in a fluidized bed dryer.
  • a particularly preferred possibility is to subject the preferably aqueous surfactant precursors to fluidized bed granulation ("SKET" granulation).
  • SKET fluidized bed granulation
  • the anionic surfactants can be used both in the dried state and as an aqueous preparation.
  • the aqueous solutions or melts of the coating materials are introduced into the fluidized bed simultaneously or in succession via one or more nozzles.
  • surfactant powder is continuously blown through a nozzle into a fluidized bed approximately filled with seed material, and the coating materials are metered in via a second nozzle. This corresponds to a continuous solid / liquid production, but presupposes that appropriately dried surfactant powder is already available.
  • the process can also be carried out continuously in liquid / liquid form.
  • care must be taken that the aqueous surfactant preparation is introduced at such a high temperature that the droplets are dried immediately after leaving the nozzle without the anionic surfactant decomposing.
  • the coating materials, especially the aqueous solutions must be injected at such a low temperature that they do not dry out immediately after leaving the nozzle, but can be deposited on the tenside particle. The conditions required for this depend in particular on the cross section of the system and can be found by the person skilled in the art by routine optimization.
  • Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m.
  • the granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s.
  • the granules are preferably discharged from the fluidized bed via a size classification of the granules.
  • the classification can take place, for example, by means of a sieve device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the inflowing air is usually composed of the heated or unheated classifier air and the heated bottom air.
  • the soil air temperature is between 80 and 400, preferably 90 and 350 ° C.
  • a starting compound for example a surfactant granulate from an earlier test batch, is advantageously introduced at the start of the granulation.
  • the water evaporates from the emulsions or dispersions, producing dried to dried germs, which are coated with further amounts of anionic surfactant, granulated and again dried at the same time.
  • the aqueous solutions of the coating substances can also be used together with the surfactant precursors, but this can lead to some of the coating materials ending up in the grain and the coating of the grain being incomplete. In some cases, this may be sufficient for the intended effect, but it is more advantageous to add the aqueous solutions to the granulation only at the end of the drying process, in order to ensure that the grain is coated very substantially.
  • German patent applications DE 4303211 A1 and DE 4303176 A1 it is also possible to use agglomerates which result from the granules caking together.
  • Another object of the present invention relates to the use of the invention Detergents as wash raw materials for the production of detergents and dishwashing detergents, preferably Those with a high anionic surfactant content (e.g. 5 to 25% by weight) and in the form of powders, granules, extrudates, agglomerates or tablets.
  • Other preferred ingredients of detergents, dishwashing detergents and cleaning agents using the inventive Additives are obtained are inorganic and organic builder substances, being inorganic Builder substances mainly with zeolites, crystalline layered silicates and amorphous silicates Builder properties and - where permissible - also phosphates such as tripolyphosphates are used.
  • the builders are preferably in the final formulations in amounts of 10 to 60 % By weight - based on the composition. If the substances are water-soluble, they come at the same time also suitable as envelopes for the inclusion of the surfactant grain. This applies, for example, to the im the following described silicates, dextrins, polyacrylates and the like.
  • the fine crystalline, synthetic and bound water-containing zeolite frequently used as a detergent builder is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P and Y are also suitable.
  • a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX® (commercial product from Condea Augusta SpA) is commercially available.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1 .
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171 .
  • Further suitable layered silicates are known, for example, from patent applications DE 2334899 A1, EP 0026529 A1 and DE 3526405 A1 . Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
  • small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1 .
  • Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • 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” is also understood to mean “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 provide 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 4400024 A1 .
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.
  • Usable organic builders 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), provided that such use is not objectionable for ecological reasons, and mixtures of 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 of these. The acids themselves 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 value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • 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. 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 2,000 to 30,000 can be used.
  • a preferred dextrin is described in British patent application GB 9419091 A1 ,
  • 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.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1 , EP 0427349 A1 , EP 0472042 A1 and EP 0542496 A1 and international patent applications WO 92/18542 , WO 93108251 , WO 93/16110 , WO 94/28030 , WO 95/07303 , WO 95/12619 and WO 95/20608 are known.
  • An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate .
  • glycerol disuccinates and glycerol trisuccinates are particularly preferred in this context, such as are described, for example, in US Pat . Nos . 4,524,009 , 4,639,325 , in European patent application EP 0150930 A1 and in Japanese patent application JP 93/339896 .
  • Suitable amounts used in formulations containing zeolite and / or silicate are from 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be 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 cobuilders are described, for example, in international patent application WO 95/20029 .
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid and measured in each case against polystyrene sulfonic 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.
  • the relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid).
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, with 20 to 55% by weight aqueous solutions being preferred.
  • Granular polymers are usually subsequently mixed into one or more basic granules.
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to DE 4300772 A1, are salts of acrylic acid and maleic acid, as well as vinyl alcohol or vinyl alcohol derivatives, or, according to DE 4221381 C2, are monomer salts of acrylic acid and the 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which are described in German patent applications DE 4303320 A1 and DE 4417734 A1 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids are also to be mentioned as further preferred builder substances. Polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1 .
  • 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.
  • the agents can also contain components that make the oil and fat washable made of textiles.
  • the preferred oil and fat-dissolving components include, for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxyl groups from 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and that from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives known from technology, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, they are particularly preferred 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, normal water glasses which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or 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.
  • the content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
  • the sodium silicate content of the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • the detergents can contain other known detergents, dishwashing detergents and cleaning agents commonly used additives, for example salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as color and Contain fragrances, opacifiers or pearlescent agents.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.
  • Bleach activators which can be used are 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. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines in particular tetraacetylethylene diamine (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 acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from German patent
  • hydrophilically substituted acylacetals known from German patent application DE 19616769 A1 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 4443177 A1 can also be used. Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446982 B1 and EP 0453 003 B1 can also be present as so-called bleaching catalysts.
  • the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 19529905 A1 and their N-analog compounds known from German patent application DE 19620267 A1 , which are known from German Patent application DE 19536082 A1 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium described in German patent application DE 196 05 688 - and copper complexes with nitrogen-containing tripod ligands known from the German patent application DE 19620411 A1 cobalt, iron, copper and ruthenium-ammine complexes, the manganese described in the German patent application DE 4416438 A1, copper and cobalt complexes, the cobalt complexes described in European patent application EP 0272030 A1, which are known from the European patent application EP 0693550 A1 manganes
  • Bleach-enhancing transition metal complexes in particular with 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% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total agent.
  • Enzymes in particular include those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and micro
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the agents can contain further enzyme stabilizers .
  • enzyme stabilizers 0.5 to 1% by weight sodium formate can be used.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • 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 cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferred. used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners .
  • Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used.
  • Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
  • Soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10.
  • the molecular weight of the linking polyethylene glycol units is in particular in the range of 750 to 5000, i.e. the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approx. 15 up to 100.
  • the polymers are characterized by an average molecular weight of approximately 5000 to 200,000 and can have a block, but preferably a random structure.
  • Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20 preferred are those polymers which link polyethylene glycol units with a molecular weight from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of Have polymers from about 10,000 to about 50,000.
  • Examples of commercially available polymers are Products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
  • Wax-like compounds can be used as defoamers .
  • Compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C., are understood to be “waxy”.
  • the waxy defoamer substances are practically insoluble in water, ie at 20 ° C. they have a solubility of less than 0.1% by weight in 100 g of water.
  • all wax-like defoamer substances known from the prior art can be contained.
  • Suitable wax-like compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols, and paraffin waxes or mixtures thereof.
  • the silicone compounds known for this purpose can of course also be used.
  • Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420 , and / or its solidification point , This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C.
  • paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
  • Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight.
  • the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures.
  • the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
  • Suitable bisamides as defoamers are those derived from saturated fatty acids with 12 to 22, preferably 14 to 18, carbon atoms and from alkylenediamines with 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bismyristoylethylenediamine, bispalmitoylethylenediamine, bisstearoylethylenediamine and their mixtures and the corresponding derivatives of hexamethylenediamine.
  • Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms.
  • these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
  • the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
  • suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
  • Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • Suitable esters of polyvalent alcohols include xylitol monopalmitate, Pentarythritmonostearat, glycerol, ethylene glycol and sorbitan, sorbitan, sorbitan Sorbitandilaurat, sorbitan, sorbitan dioleate, and also mixed tallowalkyl and diesters.
  • Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred.
  • Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
  • esters as defoamers are beeswax, which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3 , and carnauba wax , which is a mixture of camamaic acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
  • beeswax which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3
  • carnauba wax which is a mixture of camamaic acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
  • Suitable carboxylic acids as a further defoamer compound are, in particular, behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid and lauric acid, and mixtures thereof, as are obtainable from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
  • Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of the fatty acids described.
  • Dialkyl ethers may also be present as defoamers.
  • the ethers can be constructed asymmetrically or symmetrically, ie contain two identical or different alkyl chains, preferably with 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, di-ioctyl ether and di-n-stearyl ether; dialkyl ethers which have a melting point above 25 ° C., in particular above 40 ° C., are particularly suitable.
  • Suitable defoamer compounds are fatty ketones, which can be obtained by the relevant methods of preparative organic chemistry. For their preparation, one starts from, for example, carboxylic acid magnesium salts which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water, for example in accordance with German published patent application DE 2553900 OS.
  • Suitable fat ketones are those which are prepared by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, arachic acid, gadoleic acid, behenic acid or erucic acid.
  • Suitable defoamers are fatty acid polyethylene glycol esters , which are preferably obtained by base-homogeneously catalyzed addition of ethylene oxide to fatty acids.
  • the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts.
  • alkanolamines especially triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to producing low-ethoxylated compounds.
  • the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the wax-like defoamer mixture.
  • the paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble layered silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
  • the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
  • the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless a high rate of dissolution in water.
  • the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
  • the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the names Aerosil® or Sipemat® can also be used.
  • suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
  • Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
  • Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • native starch which is composed of amylose and amylopectin. Starch is referred to as native starch, as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
  • Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
  • alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
  • Suitable silicones are conventional organopolysiloxanes, which can have a content of finely divided silica, which in turn can also be silanized. Such organopolysiloxanes are described, for example, in European patent application EP 0496510 A1 . Polydiorganosiloxanes which are known from the prior art are particularly preferred. However, compounds crosslinked via siloxane can also be used, as are known to the person skilled in the art under the name silicone resins. As a rule, the polydiorganosiloxanes contain finely divided silica, which can also be silanized. Silica-containing dimethylpolysiloxanes are particularly suitable.
  • the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. in the range from 5,000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
  • the silicones are preferably applied to carrier materials. Suitable carrier materials have already been described in connection with the paraffins.
  • the carrier materials are generally present in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.
  • fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances .
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpropionate, stally.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, ⁇ -isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the agents according to the invention, but they can also be advantageous to apply the fragrances on carriers, which the adhesion of the perfume to the laundry intensify and ensure a long-lasting fragrance of the textiles through a slower fragrance release.
  • Cyclodextrins for example, have proven successful as such carrier materials, the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
  • the final preparations can also contain inorganic salts as fillers or fillers, such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.
  • inorganic salts such as sodium sulfate, which is preferably present in amounts of 0 to 10, in particular 1 to 5% by weight, based on the composition.
  • the washing, rinsing and cleaning agents obtainable using the detergents according to the invention can be produced in the form of powders, extrudates, granules, agglomerates or tablets or be used. To produce such agents, the corresponding ones are from the prior art known methods.
  • the agents are preferably prepared in that various Particulate components containing the ingredients are mixed together.
  • the particulate components can be spray dried, simple mixed or complex Granulation processes, for example fluidized bed granulation, are produced. Is preferred in particular that at least one surfactant-containing component by fluidized bed granulation will be produced. It can furthermore be particularly preferred if aqueous preparations of the alkali silicate and the alkali carbonate together with other ingredients in a drying facility can be sprayed, and granulation can take place simultaneously with the drying.
  • the drying device into which the aqueous preparation is sprayed can be any drying apparatus.
  • the drying is carried out as spray drying in a drying tower.
  • the aqueous preparations are exposed to a drying gas stream in finely divided form in a known manner.
  • Patent publications by Henkel describe an embodiment of spray drying with superheated steam. The working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention.
  • the mixtures are then subjected to a compacting step, with further Ingredients are only added to the agents after the compacting step.
  • the compacting of the ingredients takes place in a preferred embodiment of the invention in a press agglomeration process instead of.
  • the press agglomeration process to which the solid premix (dried base preparation) subject can be realized in various devices. Depending on A distinction is made between the type of agglomerator used and different press agglomeration processes.
  • the four most common press agglomeration processes preferred in the context of the present invention are extrusion, roll pressing or compacting, hole pressing (Pelletizing) and tabletting, so that preferred press agglomeration processes within the scope of the present invention Extrusion, roll compacting, pelletizing or tableting processes are.
  • binders can be used as an aid to compaction.
  • a binder is used that at temperatures up to 130 ° C, preferably up to a maximum of 100 ° C. and in particular up to 90 ° C. is already completely in the form of a melt.
  • the binder must therefore be selected depending on the process and process conditions or the process conditions, especially the process temperature - if a certain one Binder is desired - to be adapted to the binder.
  • the actual compression process is preferably carried out at processing temperatures that at least in the compression step at least the temperature of the softening point, if not correspond to the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt.
  • the process temperature in the compression step is not more than 20 ° C above the melting temperature or the upper limit of the melting range of the binder. It is technical quite possible to set even higher temperatures; but it has been shown that a Temperature difference to the melting temperature or the softening temperature of the binder of 20 ° C is generally sufficient and even higher temperatures are no additional advantages cause.
  • Such a temperature control has the other Advantage that also thermally sensitive raw materials, for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly processed without serious loss of active substance can be.
  • thermally sensitive raw materials for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly processed without serious loss of active substance can be.
  • the possibility of precise temperature control of the binder in particular in the decisive step of compression, i.e. between the mixing / homogenization of the Premix and the shape, allows an energetically very favorable and for the temperature sensitive Components of the premix extremely gentle process management, because the premix is only exposed to the higher temperatures for a short time.
  • the working tools of the press agglomerator (the screw (s) of the extruder, the roller (s) of the roller compactor and the press roller (s) of the pellet press) have a temperature of a maximum of 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C and the process temperature is 30 ° C and in particular a maximum of 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration is preferably the temperature effect in the compression area of the press agglomerators a maximum of 2 minutes and is particularly in a range between 30 seconds and 1 minute.
  • Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which again have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C 3 -C 5 glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
  • the preferably used polyethylene glycols can have a linear or branched structure, linear polyethylene glycols being preferred in particular.
  • the particularly preferred polyethylene glycols include those with relative molecular weights between 2,000 and 12,000, advantageously around 4,000, polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, and can be used Such combinations advantageously have more than 50% by weight, based on the total amount of polyethylene glycols, of polyethylene glycols with a relative molecular weight of between 3,500 and 5,000.
  • polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600.
  • these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
  • suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred.
  • Polyvinylpyrrolidones are preferably not used as sole binders but in combination with other used in particular in combination with polyethylene glycols.
  • the compacted material preferably has temperatures immediately after it leaves the production apparatus not above 90 ° C, with temperatures between 35 and 85 ° C particularly preferred are. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C, for example up to 70 ° C, are particularly advantageous.
  • the final preparations are produced by means of an extrusion , as described, for example, in European patent EP 0486592 B1 or international patent applications WO 93/02176 and WO 94/09111 or WO 98/12299 .
  • a solid premix is extruded under pressure and the strand is cut to the predeterminable size of the granulate by means of a cutting device after it has emerged from the hole shape.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers.
  • the premix is preferably fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knives.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule size. In this way, granules of an essentially uniformly predeterminable particle size can be produced, the absolute particle sizes in particular being able to be adapted to the intended use.
  • particle diameters up to at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic primary granules to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
  • extrusions / pressing can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.
  • the temperature control in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
  • the duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the agents can also be produced by means of roller compaction .
  • the premix is metered in between two smooth rollers or those provided with depressions of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example, certain shapes of the later particles can be specified.
  • the Schülpenband is subsequently broken into smaller pieces by a knock-off and crushing process and can be processed in this way to Granulkkömem, which can be refined by other known surface treatment methods, in particular brought into an approximately spherical shape.
  • the temperature of the pressing tools that is to say the rollers, is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • the duration of the temperature effect in the compression region of the smooth rollers or with recesses of a defined shape is a maximum of 2 minutes and in particular lies in a range between 30 seconds and 1 minute.
  • the final preparations can also be made by pelleting .
  • the premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization.
  • the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands, and finally comminuted into granules using a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
  • the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
  • An apparatus suitable for carrying out the method is described, for example, in German laid-open specification DE 3816842 A1 .
  • the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the temperature of the pressing tools is preferably at most 150 ° C., preferably at most 100 ° C. and in particular at a maximum of 75 ° C.
  • Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
  • Another press agglomeration process that can be used to produce the inventive is tableting. Due to the size of the tablets produced, it may be useful for tableting to add conventional disintegration aids, for example cellulose and its derivatives, in particular in coarser form, or cross-linked PVP in addition to the binder described above, which facilitate the disintegration of the compacts in the wash liquor.
  • the particulate press agglomerates obtained can either be used directly or aftertreated and / or prepared beforehand by customary methods.
  • the usual aftertreatments include, for example, powdering with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density.
  • a preferred aftertreatment is also the procedure according to German patent applications DE 19524287 A1 and DE 19547457 A1 , in which dusty or at least finely divided ingredients (the so-called fine fractions) are adhered to the particulate end products of the process, which serve as the core, and thus give rise to means , which have these so-called fines as an outer shell.
  • this advantageously takes place by melting agglomeration.
  • the solid end preparations are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
  • the base of these tablets can be circular or rectangular, for example.
  • Multi-layer tablets in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
  • the washing or rinsing agent tablets generally contain a disintegrant which is intended to bring about the rapid dissolution of the tablet or the rapid disintegration of the tablet in the aqueous liquor.
  • a disintegrant which is intended to bring about the rapid dissolution of the tablet or the rapid disintegration of the tablet in the aqueous liquor.
  • German patent applications DE 19709991 A1 and DE 19710254 A1 in which preferred cellulose-based disintegrant granules are described.
  • a fluidized bed was filled with powdered dodecylbenzenesulfonate sodium salt as the seed material with up to 70% of the fluidized bed capacity. Subsequently, at a soil air temperature of 160 ° C. (ie a temperature of approx. 95 ° C. in the fluidized bed), further surfactant powder was introduced continuously using a first nozzle. A 50% by weight aqueous sodium acetate solution was introduced through a second nozzle to coat the surfactant core. The material flows were adjusted by regularly checking the discharged and classified coated granules from the fluidized bed in such a way that the acetate content in the end product was 42% by weight.
  • Example H2 was repeated using powdered coconut alcohol sulfate sodium salt (Sulfopon® 1218 G, Cognis GmbH, Dusseldorf / FRG). The coating was carried out with a 37% by weight aqueous solution of sodium citrate dihydrate. The material flows were adjusted so that the content of sodium citrate in the end product was 20% by weight.
  • composition of detergent tablets and disintegration times composition 1 2 V1 V2 Dodecylbenzenesulfonate sodium salt acc. Ex. H1 52.0 - - - Dodecylbenzenesulfonate sodium salt - - 30.0 - Coconut fatty alcohol sulfate sodium salt acc. Ex. H2 - 38.0 - - Coconut fatty alcohol sulfate sodium salt - - - 30.0 Microcrystalline cellulose 5.0 5.0 5.0 5.0 calcium carbonate 18.0 22.0 40.0 40.0 sodium sulphate 25.0 25.0 25.0 25.0 25.0 Disintegration time [s] 7 5 22 25

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Amplifiers (AREA)
  • Control Of Motors That Do Not Use Commutators (AREA)
  • Treatment Of Sludge (AREA)

Claims (10)

  1. Détergents sous forme solide,
    caractérisés en ce qu'
    ils se composent d'un noyau de composés tensioactifs anioniques et d'une couche enveloppant ces derniers, laquelle consiste en sels hydrosolubles d'acides minéraux ou sels hydrosolubles d'acides carboxyliques organiques, à condition que les substances enveloppantes présentent une hydrosolubilité d'au moins 10 g/l à 20 °C et que les composés tensioactifs anioniques soient présents dans des proportions allant de 20 à 99 % en poids.
  2. Détergents selon la revendication 1,
    caractérisés en ce qu'
    ils contiennent en tant que noyau des composés tensioactifs anioniques choisis parmi le groupe constitué par les savons, les sulfonates d'alkylbenzène, les sulfonates d'alcanes, les sulfonates d'oléfines, les sulfonates d'éther alkylique, les sulfonates d'éther de glycérol, les sulfonates d'ester α-méthylique, les acides gras sulfonés, les alkylsulfates, les sulfates d'éther d'alcools gras, les sulfates d'éther de glycérol, les sulfates d'hydroxyéthers mixtes, les sulfates (d'éther) de monoglycérides, les sulfates (d'éther) d'amides d'acides gras, les mono- et dialkylsulfosuccinates, les mono- et dialkylsulfosuccinamates, les sulfotriglycérides, les savons amidés, les acides éther-carboxyliques et leurs sels, les iséthionates d'acides gras, les sarcosinates d'acides gras, les taurides d'acides gras, les acides N-acylaminés, les sulfates d'alkyloligoglucosides, les condensats d'acides gras de protéines et les phosphates (d'éther) d'alkyle ainsi que leurs mélanges.
  3. Détergents selon les revendications 1 et/ou 2,
    caractérisés en ce qu'
    ils contiennent en tant que noyau des alkylsulfates, des sulfonates d'alkylbenzène, des sulfonates d'oléfines, des sulfonates d'ester méthylique ainsi que leurs mélanges.
  4. Détergents selon au moins l'une quelconque des revendications 1 à 3,
    caractérisés en ce que
    les substances enveloppantes sont présentes dans des proportions allant de 1 à 80 % en poids.
  5. Procédé de production de détergents sous forme solide selon la revendication 1,
    caractérisé en ce qu'
    on sèche tout d'abord une pâte ou une solution aqueuse des composés anioniques tensioactifs, et pendant que l'eau s'évapore ou dépose sur le grain qui se forme une substance enveloppante constituée par une solution aqueuse ou une masse fondue.
  6. Procédé selon la revendication 5,
    caractérisé en ce qu'
    on soumet les pâtes ou solutions aqueuses des composés anioniques tensioactifs à un séchage par pulvérisation, on mélange intimement les poudres produites avec les solutions aqueuses ou masses fondues des substances enveloppantes et, le cas échéant, on élimine l'eau.
  7. Procédé selon la revendication 5,
    caractérisé en ce qu'
    on soumet les préparations aqueuses des composés anioniques tensioactifs et les solutions aqueuses des substances enveloppantes à un séchage et à une granulation en lit fluidisé simultanés, les préparations tensioactives aqueuses devant être amenées à une température suffisamment élevée pour permettre aux gouttelettes de sécher immédiatement après leur sortie de la filière sans que le tensioactif anionique ne se décompose, les substances enveloppantes aqueuses devant toutefois être injectées à une température suffisamment faible pour qu'elle ne sèchent pas immédiatement après leur sortie de la filière mais se déposent sur le grain tensioactif.
  8. Procédé selon la revendication 5,
    caractérisé en ce qu'
    on sèche et granule les poudres sèches des composés tensioactifs anioniques et les solutions aqueuses ou masses fondues des substances enveloppantes en lit fluidisé.
  9. Utilisation des détergents selon la revendication 1 pour la production de produits de lavage de rinçage et, de nettoyage.
  10. Utilisation selon la revendication 9 pour la production de produits de lavage, de rinçage et de nettoyage sous la forme de poudres, de granulés, d'extrudats, d'agglomérats ou de pastilles.
EP00118328A 1999-09-03 2000-08-24 Détergents sous forme solide Expired - Lifetime EP1081219B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19941934A DE19941934A1 (de) 1999-09-03 1999-09-03 Detergentien in fester Form
DE19941934 1999-09-03

Publications (3)

Publication Number Publication Date
EP1081219A2 EP1081219A2 (fr) 2001-03-07
EP1081219A3 EP1081219A3 (fr) 2001-04-25
EP1081219B1 true EP1081219B1 (fr) 2004-07-28

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ID=7920608

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Application Number Title Priority Date Filing Date
EP00118328A Expired - Lifetime EP1081219B1 (fr) 1999-09-03 2000-08-24 Détergents sous forme solide

Country Status (4)

Country Link
EP (1) EP1081219B1 (fr)
AT (1) ATE272105T1 (fr)
DE (2) DE19941934A1 (fr)
ES (1) ES2224979T3 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19946342A1 (de) * 1999-09-28 2001-04-05 Cognis Deutschland Gmbh Formkörper mit verbesserter Wasserlöslichkeit
GB2404662A (en) * 2003-08-01 2005-02-09 Reckitt Benckiser Cleaning composition
EP2441820A1 (fr) * 2010-10-14 2012-04-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Particules de détergent pour le lavage du linge
EP2441821A1 (fr) * 2010-10-14 2012-04-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Particules de détergent pour le lavage du linge
MX2013003934A (es) 2010-10-14 2013-06-28 Unilever Nv Composiciones de detergente particulado que comprenden agente fluorescente.
CA2813697C (fr) 2010-10-14 2018-08-28 Unilever Plc Fabrication de detergents particulaires enrobes
CN103154230B (zh) 2010-10-14 2015-01-21 荷兰联合利华有限公司 洗衣用洗涤剂颗粒
CN103282477B (zh) * 2010-10-14 2015-04-01 荷兰联合利华有限公司 顶部装载洗衣容器的方法
WO2012048910A1 (fr) * 2010-10-14 2012-04-19 Unilever Plc Composition de détergent particulaire conditionnée
MY164216A (en) 2010-10-14 2017-11-30 Unilever Nv Laundry detergent particles
AU2011315792B2 (en) 2010-10-14 2014-03-13 Unilever Plc Laundry detergent particle
IN2013MN00622A (fr) 2010-10-14 2015-06-12 Unilever Plc
US9273271B2 (en) 2010-10-14 2016-03-01 Conopco Inc. Laundry detergent particles

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Publication number Priority date Publication date Assignee Title
DE4303211A1 (de) * 1993-02-04 1994-08-11 Henkel Kgaa Anionische Tenside mit verbesserter Löslichkeit
EP1059350A1 (fr) * 1999-06-08 2000-12-13 Greither, Peter Composition détergente encapsulée
WO2000078912A1 (fr) * 1999-06-21 2000-12-28 The Procter & Gamble Company Procede d'enrobage de granules de detergent dans un lit fluidise

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JPH07286199A (ja) * 1994-04-15 1995-10-31 Lion Corp タブレット洗剤組成物の製造方法
DE4415369C1 (de) * 1994-05-02 1995-08-31 Henkel Kgaa Heterogene Tensidgranulate
DE4429550A1 (de) * 1994-08-19 1996-02-22 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten
JPH09302395A (ja) * 1996-05-14 1997-11-25 Lion Corp 界面活性剤粉体、粒状洗剤組成物およびその製造方法
DE19721708A1 (de) * 1997-05-23 1998-11-26 Henkel Kgaa Verkapseltes Reinigungsmittel
TR200001042T2 (tr) * 1997-10-22 2000-08-21 Unilever N.V. Tablet şeklindeki deterjan bileşikleri

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Publication number Priority date Publication date Assignee Title
DE4303211A1 (de) * 1993-02-04 1994-08-11 Henkel Kgaa Anionische Tenside mit verbesserter Löslichkeit
EP1059350A1 (fr) * 1999-06-08 2000-12-13 Greither, Peter Composition détergente encapsulée
WO2000078912A1 (fr) * 1999-06-21 2000-12-28 The Procter & Gamble Company Procede d'enrobage de granules de detergent dans un lit fluidise

Also Published As

Publication number Publication date
ES2224979T3 (es) 2005-03-16
DE19941934A1 (de) 2001-03-15
DE50007182D1 (de) 2004-09-02
EP1081219A3 (fr) 2001-04-25
ATE272105T1 (de) 2004-08-15
EP1081219A2 (fr) 2001-03-07

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