EP0344629B1 - Granular adsorption material with improved flushing property - Google Patents

Granular adsorption material with improved flushing property Download PDF

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Publication number
EP0344629B1
EP0344629B1 EP89109494A EP89109494A EP0344629B1 EP 0344629 B1 EP0344629 B1 EP 0344629B1 EP 89109494 A EP89109494 A EP 89109494A EP 89109494 A EP89109494 A EP 89109494A EP 0344629 B1 EP0344629 B1 EP 0344629B1
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EP
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Prior art keywords
weight
adsorbent
water
sodium
acid
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EP89109494A
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German (de)
French (fr)
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EP0344629A1 (en
Inventor
Elmar Dr. Wilms
Lothar Pioch
Günther Dr. Vogt
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT89109494T priority Critical patent/ATE98294T1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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

Definitions

  • the invention relates to a granular adsorbent with a high absorption capacity for liquid to pasty detergent and cleaning agent components, in particular liquid or melting non-ionic surfactants when heated, which is particularly suitable for use in phosphate-free or low-phosphate detergents and cleaning agents. It has a significantly improved flushing behavior, i.e. it does not form undissolved residues in the washing-in devices of automatic washing machines and moreover improves the washing-in behavior of detergent mixtures in such devices.
  • nonionic surfactants have a very high cleaning power, which makes them particularly suitable for use in cold detergents or 60 ° C. detergents.
  • their proportion cannot be increased significantly beyond 8 to 10 percent by weight in the generally customary production of detergents by spray drying, since otherwise there is excessive smoke formation in the exhaust air from the spray towers and poor pouring properties of the spray powder.
  • Methods have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried powder or sprayed onto a carrier substance.
  • Loose in particular spray-dried phosphates, borates or perborate, sodium aluminosilicate (zeolite), silicon dioxide (Aerosil®) or salt mixtures previously prepared in a certain manner, e.g. those proposed from sodium carbonate and sodium bicarbonate, but all known agents have certain disadvantages.
  • Phosphates are often undesirable because of their eutrophic properties.
  • Borates or perborates have only a limited absorption capacity for liquid substances, which also applies to finely powdered zeolites, while special adsorbents such as diatomaceous earth and Aerosil® as inert components do not contribute to the washing effect.
  • EP-A-50 894 describes water softening agents containing zeolite, an agglomerating agent such as polyethylene glycol, organic salts and essentially unsaturated fatty acid soap. A content of (co) polymeric acrylic acids or acrylates is neither described nor suggested. The use of such agents as adsorbents is not known.
  • Absorbent carrier grains which consist of several components and are usually produced by spray drying, are e.g. known from US-A-3 849 327, US-A-3 886 098 and US-A-3 383 027 and US-A-4 269 722 (DE-A-27 42 683).
  • these carrier grains developed especially for the adsorption of nonionic surfactants, contain considerable amounts of phosphates, which limits their possible uses.
  • Phosphate-free carrier grains are known from DE-A-32 06 265. They consist of 25 to 52% sodium carbonate or hydrogen carbonate, 10 to 50% zeolite, 0 to 18% sodium carbonate and 1 to 20% bentonite or 0.05 to 2% polyacrylate.
  • the high proportion of carbonate favors the formation of calcium carbonate in hard water and thus the formation of incrustations on the textile fiber or the heating elements in the washing machine.
  • the absorption capacity of the carrier grains cited above is limited. If more than 25% by weight of liquid or sticky nonionic surfactants are mixed, the free-flowing properties of the products decrease considerably and are unsatisfactory above 30% by weight.
  • EP-A-184 794 discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight.
  • -% of nonionic surfactants and is available by spray drying. In practice, it has been shown that in washing machines with poorly designed washing-in devices, the products do not completely detach during the washing-in phase and leave residues.
  • EP-A-289 767 published on November 9, 2008, describes granular adsorbents which contain 60 to 80% by weight of zeolite, 0.1 to 8% by weight of sodium silicate, 3 to 15% by weight of a mixture of two different ones Contain acrylic acid polymers with different viscosity numbers, 8 to 18 wt .-% water removable at a drying temperature of 145 ° C and optionally nonionic surfactants. No soap content is disclosed.
  • Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% particles smaller than 10 ⁇ m. Their average particle size (volume distribution, measurement method: Coulter Counter) is in the range from 1 to 10 ⁇ m.
  • Their calcium binding capacity, which is determined according to the information in DE-A-24 12 837, is in the range from 100 to 200 mg CaO / g. The zeolites can still contain excess alkali from their production.
  • Component (b) consists of a water-soluble soap, preferably a sodium soap, which is derived from essentially saturated fatty acids with 12 to 24, preferably 14 to 22, carbon atoms, and mixtures thereof with oleic acid, the proportion of saturated fatty acids being at least 50 % By weight, preferably at least 75% by weight.
  • a water-soluble soap preferably a sodium soap
  • saturated fatty acids being at least 50 % By weight, preferably at least 75% by weight.
  • soaps made from coconut oil, tallow oil and hardened rapeseed oil fatty acids, hardened fish oil fatty acids and mixtures thereof. Their proportion is 1.0 to 6, preferably 1.5 to 5 and in particular 2 to 4% by weight.
  • the component (c) consists of a homopolymeric and / or copolymeric acrylic acid, methacrylic acid and / or maleic acid or their water-soluble salts, for example sodium or potassium salt, the sodium salts being preferred.
  • Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid.
  • Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
  • copolymeric acids in which one of the components has no acid function the proportion thereof, in the interest of sufficient water solubility, is not more than 70 mole percent, preferably less than 50 mole percent.
  • Copolymers of acrylic acid or methacrylic acid with maleic acid as described in more detail in EP 25 551-B1, have proven to be particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
  • the molecular weight of the homo- or copolymers is generally 2,000 to 150,000, preferably 5,000 to 100,000.
  • Their proportion of the adsorbent is 1 to 12% by weight, preferably 1.5 to 8% by weight and in particular 2 to 5% by weight, calculated as the sodium salt.
  • the resistance of the grains to abrasion increases with an increasing proportion of polyacid or its salts. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases. Mixtures with 2 to 5% by weight of sodium salt of polyacid have optimal abrasion properties.
  • the weight ratio of soap (b) to polymeric acid sodium salt (c) is in the range from 2.5: 1 to 1: 5, in particular in the range from 1.5: 1 to 1: 4 . These areas are characterized by good induction results. Stronger Deviations, especially higher soap contents at the expense of the polymer acid content, lead to less favorable values.
  • the sodium sulfate (component d), calculated as an anhydrous substance, is present in proportions from 0 to 25% by weight, preferably from 0.5 to 22 and in particular from 3 to 20% by weight.
  • the sodium sulfate can contribute to a considerable improvement in the grain structure and the flushing behavior of the agents and at the same time increases their bulk density, which makes it possible to save packaging and transport volume.
  • the adsorbent can contain nonionic surfactants in proportions of up to 5% by weight, preferably 0 to 4% by weight, and in particular 0.3 to 3% by weight.
  • Suitable nonionic surfactants are, in particular, ethoxylation products of linear or methyl-branched (oxo radical) alcohols with 12 to 18 carbon atoms and 3 to 10 ethylene glycol ether groups. Also useful are ethoxylation products of vicinal diols, amines, thioalcohols and fatty acid amides, which correspond to the fatty alcohol ethoxylates described with regard to the number of carbon atoms in the hydrophobic radical and the glycol ether groups.
  • Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups can also be used.
  • block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics are also suitable.
  • the nonionic surfactants can then be present if aqueous zeolite dispersions in which these surfactants function as dispersion stabilizers are used in the production of the granular adsorbents. In individual cases, the nonionic surfactants can also be completely or partially replaced by other dispersion stabilizers, as described in DE-A-25 27 388 (US-A-4 072 622).
  • water 10 to 24% by weight of the adsorbent is accounted for by water, which is present in bound form and as moisture, the major amount being bound to the zeolite.
  • a proportion of the water which is about 8 to 18 wt .-% (based on the agent), can be removed at a drying temperature of 145 ° C.
  • Another portion which is between 4 and 8% by weight depending on the zeolite portion, is released at the annealing temperature (800 ° C.) and corresponds to the water stored in the crystal lattice of the zeolite.
  • the average grain size of the adsorbent is 0.2 to 1.2 mm, the proportion of the grains being less than 0.05 mm less than 1% by weight, preferably less than 0.5% by weight and not more than 2 mm Is 5% by weight.
  • at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.1 to 1.2 mm, the proportion of the grains between 0.1 and 0.05 mm preferably not more than 3 %
  • the proportion of the grains between 0.1 and 0.2 by less than 20% by weight, in particular less than 10% by weight and the proportion of the grains between 1, 2 and 2 mm is not more than 10% by weight, in particular not more than 5% by weight.
  • the bulk density of the adsorbent is 350 to 680 g / l, preferably 400 to 650 g / l.
  • the agent essentially consists of rounded grains, which have a very good flow behavior. This very good flow behavior is still present when the grains are impregnated with large proportions of liquid or semi-liquid detergent components, especially nonionic surfactants.
  • the proportion of these adsorbed components can be 10 to 35% by weight, preferably 15 to 30% by weight, based on the adsorbate.
  • the invention further relates to a method for producing the granular adsorbent according to the invention.
  • This The process is characterized in that an aqueous mixture comprising the components (a) to (c) and, if appropriate, the components (d), (e) and additional alkali metal hydroxide, with a total of 40 to 55% by weight of anhydrously calculated ingredients Sprayed nozzles into a drop room and dried to a moisture content of 8 to 18% by weight that can be removed at 145 ° C. by means of drying gases which have an inlet temperature of 150 to 280 ° C. and an outlet temperature of 50 to 120 ° C.
  • the aqueous batch can be prepared by mixing the dry or water-containing constituents with the addition of the water required for liquefaction.
  • the zeolite can be used as a spray-dried powder or granulate or as a water-containing filter cake or as an aqueous dispersion. If spray-dried zeolite granules are used as the starting material, these may already contain polymers and / or the sodium sulfate or a proportion thereof. Instead of the soap or the salts of the polymeric carboxylic acids, the corresponding free acids can also be incorporated and the alkali required for salt formation can be added separately.
  • alkali hydroxide in particular NaOH
  • NaOH alkali hydroxide
  • the content of anhydrous ingredients in the aqueous mixture is preferably 43 to 50% by weight. Its temperature is advantageously 50 to 100 ° C and its viscosity 2,000 to 20,000 mPa ⁇ s, usually from 8,000 to 14,000 mPa ⁇ s.
  • the atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar.
  • the drying gas which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent.
  • the inlet temperature measured in the ring channel (ie immediately before entering the lower part of the tower), is 150 to 280 ° C, preferably 170 to 250 ° C .
  • the exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 130 ° C., preferably 55 to 115 ° C.
  • the adsorbent is to be impregnated with nonionic surfactants, these can be sprayed onto the spray product which is still warm or onto the spray product which has already cooled or which has been heated again after cooling. Heating the nonionic surfactant to temperatures between 35 and 60 ° C, preferably 40 to 50 ° C, accelerates the adsorption process.
  • the abrasion resistance and constancy of shape of the grains is so high if the specified proportions or manufacturing conditions are observed that even the freshly prepared, but especially the cooled and, if necessary, reheated, matured grains are treated, mixed and conveyed with the liquid additives under the usual spray mixing conditions can be made without the formation of fine fractions or coarser agglomerates.
  • Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be present in proportions of 0.03 to 3, preferably 0.05 to 2% by weight, based on that with the additive loaded adsorbents are used. For example, B.
  • finely powdered zeolites silica airgel (Aerosil (R) ), colorless or colored pigments, such as titanium dioxide and other powder materials already proposed for powdering granules or detergent particles, such as finely powdered sodium tripolyphosphate, sodium sulfate, magnesium silicate and carboxylmethyl cellulose.
  • such treatment is generally not necessary, especially since the ability to be washed in is not improved thereby.
  • the additives to be adsorbed can consist of known nonionic surfactants, as are usually used in washing and cleaning agents.
  • suitable additives are organic solvents, with which the cleaning ability of detergents and cleaning agents is improved, in particular with regard to greasy soiling, and which can be incorporated into a granular cleaning agent without problems in this way.
  • sensitive substances such as enzymes, biocides, fragrances, bleach activators, softening agents, optical brighteners and anionic or cationic surfactants can be added to the adsorbents after they have been dissolved or dispersed in organic solvents or the liquid or melted nonionic surfactants. These substances come together with the solvent or dispersant in the porous grain and are thus protected against interactions with other powder components.
  • Preferred detergent constituents which are bound to the adsorbent and are present together with this as a free-flowing mixture are liquid to pasty nonionic surfactants from the class of the polyglycol ethers, derived from alcohols having 10 to 22, in particular 12 to 18, carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
  • EO ethylene oxide
  • PO propylene oxide
  • the number of EO or PO groups corresponds to the statistical mean for technical alkoxylates.
  • ethoxylated fatty alcohols examples include C12 ⁇ 18 coconut alcohols with 3 to 12 EO, C16 ⁇ 18 tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures. From the series of ethoxylated oxo alcohols, for example, those of the composition C12 ⁇ 15 + 5 to 10 EO and C14-C15 + 6 to 12 EO are suitable.
  • Mixtures of low and highly ethoxylated alcohols are distinguished by an increased detergency against both greasy and mineral soiling, for example those from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or C13 ⁇ 15Oxoalcohol + 3 to 5 EO and C12 ⁇ 14 -Oxo alcohol + 8 to 12 EO.
  • Agents in which the adsorbed nonionic surfactants have both long hydrophobic residues and higher degrees of ethoxylation have particularly favorable flushing properties.
  • nonionic surfactants additionally contain a compound which is difficult or not soluble in water, but does have a dispersible polar, hydrophobic radical. Examples of this are free, soap-forming fatty acids.
  • Partial esters of polyhydric alcohols such as partial glycerides and fatty acid glycol esters, fatty acid amides, fatty acid partial amides of alkylenediamines and hydroxyalkylalkylenediamines, fatty amines, quaternary ammonium bases or their salts, fatty alcohols and poorly soluble anionic surfactants, such as the di-salts of alphasulfo fatty acids. Mixtures of such poorly soluble or insoluble compounds can also be used.
  • the number of carbon atoms in the hydrophobic radicals should be at least 10, usually 12 to 18.
  • the quantitative ratios of nonionic surfactant to sparingly soluble additional compound is 99: 1 to 70:30. It is essential for the success that the nonionic surfactant and additive are mixed together beforehand. A successive application of the individual substances to the adsorbent does not lead to an improvement in the solubility and flushing behavior.
  • Preferred examples of this group are coconut oil, tallow and rapeseed oil fatty acids, which can also be hardened, mixtures of tallow fatty acid partial glyceride and the tallow fatty acid partial amide of hydroxyethyl-ethylenediamine, di-tallow-alkyl-dimethyl-ammonium chloride and the disodium salt of alpha-sulfo fatty acids derived from hardened C12 ⁇ 18 fatty acids.
  • the granular adsorbents impregnated with the nonionic surfactants or with the mixtures of nonionic surfactant and additive can be mixed with further powdery to granular detergents or detergent components, such as, for example are obtainable by spray drying or granulation, or can also be mixed with bleaches or with bleach-containing detergents of known composition in any ratio.
  • granular detergents or detergent components such as, for example are obtainable by spray drying or granulation
  • bleaches or with bleach-containing detergents of known composition in any ratio.
  • their good flowability and their high grain stability are of great advantage, since an undesirable formation of abrasion and dust is avoided.
  • the powder mixtures are in turn stable in storage and do not tend to clump or exude the nonionic surfactant. When used, they are particularly easy to flush in compared to known agents.
  • the liter weight was 563 g / l.
  • Dry sea sand with the following grain spectrum was chosen as the reference substance. mm over 1.5 to 0.8 to 0.4 up to 0.2 to 0.1 % By weight 0.2 11.9 54.7 30.1 3.1
  • the run-off time of the dry sand after opening the outflow opening was set at 100%.
  • the pourability of the products according to the invention is given in%, based on this 100% value. Values above 75% are considered very good.
  • a and B values are very good to satisfactory in practice.
  • C values indicate inadequate induction behavior.
  • the adsorbent had a flushing grade of A 5.
  • 2 series of tests were carried out, with the impregnated adsorbent without the addition of a detergent and a mixture of 25 parts of the impregnated adsorbent and 75 parts of a detergent, consisting of 50 parts of tower spray powder, 20 parts of sodium perborate and 5 parts of other granular constituents Defoamers, enzymes, fragrances and bleach activators (called "with W").
  • the tower spray powder had the following composition (in% by weight): 17.6% n-dodecylbenzenesulfonate (Na salt) 2.5% tallow soap (Na salt) 4.0% tallow alcohol + 14 EO 20.5% zeolite NaA (calculated anhydrous) 15.0% soda 5.0% copolymer (b) 0.5% Na hydroxyethane diphosphonate 3.0% sodium silicate 1: 3.3 1.6% carboxymethyl cellulose 18.0% sodium sulfate 12.3% water
  • Table example Flowability Induction behavior without W with W 1 82 B 2 A 8 2nd 81 B 1 A 6 3rd 80 A 5 A 5 4th 80 A 6 A 4 V1 58 C 48 C 11 V2 80 C 48 C 40
  • Example 2 As described in Example 1, 84 pbw of the adsorbent were impregnated in a spray mixer with 16 pbw of a molten surfactant mixture according to Example 2. The bulk weight of the product was 710 g / l, the flow behavior 80% and the wash-in test A8. A mixture of 20 pbw of these granules, 80 pbw of the spray-dried detergent used in Examples 1-4, 15 pbw of sodium perborate and 5 pbw of other granular constituents gave the induction test value A6 under the same test conditions.
  • the product had a bulk density of 580 g / l with the following particle size distribution: mm over 1.6 to 0.8 to 0.4 up to 0.2 to 0.1 less than 0.1 % By weight 0 8th 38 50 4th 0
  • aqueous slurry was prepared using spray dried zeolite granules. These granules consisted of a mixture of zeolite (with a removable one at annealing temperature Water content of 20% by weight) and from anhydrous sodium sulfate. Na polyacrylate (MW 32,000), coconut tallow soap and sodium hydroxide were also added to the slurry. The water content of the slurry was 52.5% by weight (including the water bound to the zeolite). The slurry, which had a temperature of 88 ° C., was spray-dried in the spray tower by the countercurrent method, the drying gases having an inlet temperature of 130 ° C. and an outlet temperature of 67 ° C.
  • the granules had the following composition (in% by weight): 59.0% zeolite (anhydrous) 0.6% NaOH 2.4% soap 2.5% Na polyacrylate 18.0% sodium sulfate 17.5% water Grain size 1.2 to 0.1 mm, average grain size 0.3 g / l, bulk density 600 g / l.
  • zeolite anhydrous
  • Na polyacrylate 18.0% sodium sulfate 17.5%
  • Grain size 1.2 to 0.1 mm, average grain size 0.3 g / l, bulk density 600 g / l.

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Abstract

PCT No. PCT/EP89/00587 Sec. 371 Date Dec. 3, 1990 Sec. 102(e) Date Dec. 3, 1990 PCT Filed May 26, 1989 PCT Pub. No. WO89/12087 PCT Pub. Date Dec. 14, 1989.A granular mixture produced by spray drying of (a) 45 to 75% by weight zeolite, (b) 1 to 6% by weight of a water soluble soap of substantially saturated C12-18 fatty acids, (c) 1 to 12% by weight homopolymers or copolymers of acrylic acid, methacrylic acid or maleic acid or water-soluble salts thereof, expressed as sodium salt, (d) 0 to 25% by weight sodium sulfate, (e) 0 to 5% by weight surfactants of the nonionic polyglycol ether derivative type, (f) 10 to 22% by weight water, has an average particle size of 0.2 to 1.2 mm and an apparent density of 350 to 680 g/l. The product, which may be used as a detergent additive, has a high adsorption capacity for liquid to paste-form detergent constituents, more particularly nonionic surfactants, and improved flushing behavior when used in domestic washing machines.

Description

Die Erfindung betrifft ein körniges Adsorptionsmittel mit hohem Aufnahmevermögen für flüssige bis pastöse Wasch- und Reinigungsmittelbestandteile, insbesondere flüssige bzw. bei Erwärmen schmelzende nichtionische Tenside, das sich vorzüglich für den Einsatz in phosphatfreien bzw. phosphatarmen Wasch- und Reinigungsmitteln eignet. Es besitzt ein wesentlich verbessertes Einspülverhalten, d.h. es bildet keine ungelösten Rückstände in den Einspülvorrichtungen von Waschautomaten und verbessert darüber hinaus das Einspülverhalten von Waschmittelgemischen in derartigen Vorrichtungen.The invention relates to a granular adsorbent with a high absorption capacity for liquid to pasty detergent and cleaning agent components, in particular liquid or melting non-ionic surfactants when heated, which is particularly suitable for use in phosphate-free or low-phosphate detergents and cleaning agents. It has a significantly improved flushing behavior, i.e. it does not form undissolved residues in the washing-in devices of automatic washing machines and moreover improves the washing-in behavior of detergent mixtures in such devices.

Nichtionische Tenside besitzen bekanntlich ein sehr hohes Reinigungsvermögen, was sie insbesondere zur Verwendung in Kaltwaschmitteln bzw. 60 °C-Waschmitteln geeignet macht. Ihr Anteil läßt sich bei der allgemein üblichen Waschmittelherstellung mittels Sprühtrocknung jedoch nicht wesentlich über 8 bis 10 Gewichtsprozent hinaus steigern, da es sonst zu einer übermäßigen Rauchbildung in der Abluft der Sprühtürme sowie mangelhaften Rieseleigenschaften des Sprühpulvers kommt. Es wurden daher Verfahren entwickelt, bei denen das flüssige bzw. geschmolzene nichtionische Tensid auf das zuvor sprühgetrocknete Pulver aufgemischt bzw. auf eine Trägersubstanz aufgesprüht wird. Als Trägersubstanz wurden lockere, insbesondere sprühgetrocknete Phosphate, Borate bzw. Perborat, Natriumalumosilikat (Zeolith), Siliciumdioxid (Aerosil®) oder in bestimmter Weise zuvor hergestellte Salzgemische, z.B. solche aus Natriumcarbonat und Natriumbicarbonat vorgeschlagen, jedoch weisen alle bekannten Mittel gewisse Nachteile auf. Phosphate sind wegen ihrer eutrophierenden Eigenschaften vielfach unerwünscht. Borate bzw. Perborate besitzen ein nur beschränktes Aufnahmevermögen für flüssige Stoffe, was auch für feinpulvrige Zeolithe gilt, während spezielle Adsorptionsmittel, wie Kieselgur und Aerosil® als inerte Bestandteile keinen Beitrag zur Waschwirkung liefern.As is known, nonionic surfactants have a very high cleaning power, which makes them particularly suitable for use in cold detergents or 60 ° C. detergents. However, their proportion cannot be increased significantly beyond 8 to 10 percent by weight in the generally customary production of detergents by spray drying, since otherwise there is excessive smoke formation in the exhaust air from the spray towers and poor pouring properties of the spray powder. Methods have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried powder or sprayed onto a carrier substance. Loose, in particular spray-dried phosphates, borates or perborate, sodium aluminosilicate (zeolite), silicon dioxide (Aerosil®) or salt mixtures previously prepared in a certain manner, e.g. those proposed from sodium carbonate and sodium bicarbonate, but all known agents have certain disadvantages. Phosphates are often undesirable because of their eutrophic properties. Borates or perborates have only a limited absorption capacity for liquid substances, which also applies to finely powdered zeolites, while special adsorbents such as diatomaceous earth and Aerosil® as inert components do not contribute to the washing effect.

Die EP-A-50 894 beschreibt wasserenthärtende Mittel, die Zeolith, ein Agglomerierungsmittel wie Polyethylenglykol, organische Salze und im wesentlichen ungesättigte Fettsäureseife enthalten. Ein Gehalt an (co-)polymeren Acrylsäuren bzw. Acrylaten wird weder beschrieben noch nahegelegt. Die Verwendung derartiger Mittel als Adsorptionsmittel ist nicht bekannt.EP-A-50 894 describes water softening agents containing zeolite, an agglomerating agent such as polyethylene glycol, organic salts and essentially unsaturated fatty acid soap. A content of (co) polymeric acrylic acids or acrylates is neither described nor suggested. The use of such agents as adsorbents is not known.

Saugfähige Trägerkörner, die aus mehreren Bestandteilen bestehen und zumeist durch Sprühtrockung hergestellt werden, sind z.B. aus US-A-3 849 327, US-A-3 886 098 und US-A-3 383 027 sowie US-A-4 269 722 (DE-A-27 42 683) bekannt. Diese insbesondere zur Adsorption von nichtionischen Tensiden entwickelten Trägerkörner enthalten jedoch erhebliche Mengen an Phosphaten, was ihre Einsatzmöglichkeiten einschränkt. Phosphatfreie Trägerkörner sind aus DE-A-32 06 265 bekannt. Sie bestehen aus 25 bis 52 % Natriumcarbonat bzw. -hydrogencarbonat, 10 bis 50 % Zeolith, 0 bis 18 % Natriumcarbonat und 1 bis 20 % Bentonit bzw. 0,05 bis 2 % Polyacrylat. Der hohe Anteil an Carbonat begünstigt jedoch eine Ausbildung von Calciumcarbonat in hartem Wasser und damit die Bildung von Inkrustationen auf der Textilfaser bzw. den Heizelementen in der Waschmaschine. Außerdem ist das Aufnahmevermögen der vorstehend zitierten Trägerkörner begrenzt. Bei Anteilen von mehr als 25 Gew.-% aufgemischten flüssigen bzw. klebrigen nichtionischen Tensiden nimmt die Rieselfähigkeit der Produkte erheblich ab und ist oberhalb 30 Gewichtsprozent unbefriedigend.Absorbent carrier grains, which consist of several components and are usually produced by spray drying, are e.g. known from US-A-3 849 327, US-A-3 886 098 and US-A-3 383 027 and US-A-4 269 722 (DE-A-27 42 683). However, these carrier grains, developed especially for the adsorption of nonionic surfactants, contain considerable amounts of phosphates, which limits their possible uses. Phosphate-free carrier grains are known from DE-A-32 06 265. They consist of 25 to 52% sodium carbonate or hydrogen carbonate, 10 to 50% zeolite, 0 to 18% sodium carbonate and 1 to 20% bentonite or 0.05 to 2% polyacrylate. However, the high proportion of carbonate favors the formation of calcium carbonate in hard water and thus the formation of incrustations on the textile fiber or the heating elements in the washing machine. In addition, the absorption capacity of the carrier grains cited above is limited. If more than 25% by weight of liquid or sticky nonionic surfactants are mixed, the free-flowing properties of the products decrease considerably and are unsatisfactory above 30% by weight.

Aus EP-A-184 794 (US-A-4 707 290) ist ein körniges Adsorptionsmittel bekannt, das hohe Anteile an flüssigen bis pastösen Waschmittelbestandteilen, insbesondere nichtionischen Tensiden aufzunehmen vermag und (auf wasserfreie Substanz bezogen) aus 60 bis 80 Gew.-% Zeolith, 0,1 bis 8 Gew.-% Natriumsilikat, 3 bis 15 Gew.-% an Homo- oder Copolymeren der Acrylsäure, Methacrylsäure und/oder Maleinsäure, 8 bis 18 Gew.-% Wasser und gegebenenfalls bis zu 5 Gew.-% an nichtionischen Tensiden enthält und durch Sprühtrocknung erhältlich ist. In der Praxis hat sich gezeigt, daß in Waschmaschinen mit ungünstig konstruierten Einspülvorrichtungen sich die Produkte im Verlauf der Einspülphase nicht vollständig lösen und Rückstände hinterlassen. Dieses verschlechterte Einspülverhalten zeigen nicht nur die betreffenden Partikel selbst, vielmehr können sie auch einen Einfluß auf die Löslichkeit bzw. das Einspülverhalten der übrigen pulverförmigen Waschmittelkomponenten ausüben. Das hat zur Folge, daß ein an sich gut einspülbares Pulvergemisch insgesamt schlecht einspülbar wird, wenn es zusätzlich eine derartige Pulverkomponente im Gemisch enthält.EP-A-184 794 (US-A-4 707 290) discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight. % Zeolite, 0.1 to 8% by weight sodium silicate, 3 to 15% by weight of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18% by weight water and optionally up to 5% by weight. -% of nonionic surfactants and is available by spray drying. In practice, it has been shown that in washing machines with poorly designed washing-in devices, the products do not completely detach during the washing-in phase and leave residues. This worsened washing-in behavior is not only shown by the particles themselves, but rather can also have an influence on the solubility or the washing-in behavior of the other powdered detergent components. The result of this is that a powder mixture which is intrinsically easy to flush in becomes difficult to flush in overall if it additionally contains such a powder component in the mixture.

Die EP-A-289 767, am 09.11.88 veröffentlicht, beschreibt körnige Adsorptionsmittel, die 60 bis 80 Gew.-% Zeolith, 0,1 bis 8 Gew.-% Natriumsilikat, 3 bis 15 Gew.-% eines Gemisches zweier verschiedener Acrylsäurepolymerisate mit unterschiedlicher Viskositätszahl, 8 bis 18 Gew.-% bei einer Trocknungstemperatur von 145 °C entfernbares Wasser sowie gegebenenfalls Niotenside enthalten. Ein Gehalt an Seife wird nicht offenbart.EP-A-289 767, published on November 9, 2008, describes granular adsorbents which contain 60 to 80% by weight of zeolite, 0.1 to 8% by weight of sodium silicate, 3 to 15% by weight of a mixture of two different ones Contain acrylic acid polymers with different viscosity numbers, 8 to 18 wt .-% water removable at a drying temperature of 145 ° C and optionally nonionic surfactants. No soap content is disclosed.

Es bestand die Aufgabe, ein körniges Adsorptionsmittel zu entwickeln, das die aufgeführten Nachteile vermeidet, ein hohes Adsorptionsvermögen aufweist und ein verbessertes Einspülverhalten besitzt. Gegenstand der Erfindung ist demnach ein körniges Adsorptionsmittel mit hohem Aufnahmevermögen für flüssige bis pastöse Wasch- und Reinigungsmittelbestandteile und verbessertem Einspülverhalten, bestehend im wesentlichen aus

  • (a) 45 bis 75 Gew.-% (als wasserfreie Substanz gerechnet) eines zum Kationenaustausch befähigten, feinkristallinen, synthetischen, gebundenes Wasser enthaltenden Natriumalumosilikats vom Typ des Zeoliths NaA sowie dessen Gemischen mit Zeolith NaX,
  • (b) 1 bis 6 Gew.-% Seife, abgeleitet von im wesentlichen gesättigten Fettsäuren mit 12 bis 24 C-Atomen in Form der Natrium- und/oder Kaliumseife,
  • (c) 1 bis 12 Gew.-% einer homo- oder copolymeren Acrylsäure, Methacrylsäure und/oder Maleinsäure sowie deren wasserlöslichen Salze, berechnet als Natriumsalz,
  • (d) 0 bis 25 Gew.-% Natriumsulfat,
  • (e) 0 bis 5 Gew.-% eines nichtionischen, Polyglykolethergruppen aufweisenden Tensids,
  • (f) 10 bis 24 Gew.-% Wasser,
wobei das Adsorptionsmittel eine mittlere Korngröße von 0,2 bis 1,2 mm aufweist und der Anteil mit einer Korngröße von weniger als 0,05 mm weniger als 1 Gewichtsprozent und der Anteil mit einer Korngröße von mehr als 2 mm nicht mehr als 5 Gew.-% und das Schüttgewicht 350 bis 680 g/l beträgt.The object was to develop a granular adsorbent which avoids the disadvantages listed, has a high adsorption capacity and has an improved washing-in behavior. The invention accordingly relates to a granular adsorbent with a high absorption capacity for liquid to pasty detergent and cleaning agent components and improved induction behavior, consisting essentially of
  • (a) 45 to 75% by weight (calculated as an anhydrous substance) of a finely crystalline, synthetic, bound water containing sodium aluminosilicate of the zeolite NaA type and its mixtures with zeolite NaX capable of cation exchange,
  • (b) 1 to 6% by weight of soap, derived from essentially saturated fatty acids with 12 to 24 carbon atoms in the form of sodium and / or potassium soap,
  • (c) 1 to 12% by weight of a homo- or copolymeric acrylic acid, methacrylic acid and / or maleic acid and their water-soluble salts, calculated as the sodium salt,
  • (d) 0 to 25% by weight sodium sulfate,
  • (e) 0 to 5% by weight of a nonionic surfactant containing polyglycol ether groups,
  • (f) 10 to 24% by weight of water,
wherein the adsorbent has an average grain size of 0.2 to 1.2 mm and the portion with a grain size of less than 0.05 mm less than 1 percent by weight and the portion with a grain size of more than 2 mm not more than 5 wt. -% and the bulk density is 350 to 680 g / l.

Der Bestandteil (a), der in Anteilen von 45 bis 75, vorzugsweise 50 bis 70 Gew.-% und insbesondere 55 bis 68 Gew.-% anwesend ist, besteht aus synthetischem, gebundenes Wasser enthaltendem Natriumalumosilikat, vorzugsweise vom Zeolith A-Typ. Brauchbar sind ferner Gemische aus Zeolith NaA und NaX, wobei der Anteil des Zeoliths NaX in derartigen Gemischen zweckmäßigerweise unter 30 %, insbesondere unter 20 %, liegt. Geeignete Zeolithe weisen keine Teilchen mit einer Größe über 30 µm auf und bestehen zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 µm. Ihre mittlere Teilchengröße (Volumenverteilung, Meßmethode: Coulter Counter) liegt im Bereich von 1 bis 10 µm. Ihr Calciumbindevermögen, das nach den Angaben der DE-A-24 12 837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g. Die Zeolithe können von ihrer Herstellung her noch überschüssiges Alkali enthalten.The component (a), which is present in proportions of 45 to 75, preferably 50 to 70% by weight and in particular 55 to 68% by weight, consists of synthetic, bound water-containing sodium aluminosilicate, preferably of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%, in particular less than 20%. Suitable zeolites have no particles larger than 30 µm and consist of at least 80% particles smaller than 10 µm. Their average particle size (volume distribution, measurement method: Coulter Counter) is in the range from 1 to 10 µm. Their calcium binding capacity, which is determined according to the information in DE-A-24 12 837, is in the range from 100 to 200 mg CaO / g. The zeolites can still contain excess alkali from their production.

Der Bestandteil (b) besteht aus einer wasserlöslichen Seife, bevorzugt einer Natriumseife, die sich von im wesentlichen gesättigten Fettsäuren mit 12 bis 24, vorzugsweise 14 bis 22 C-Atomen, sowie deren Gemischen mit Ölsäure ableitet, wobei der Anteil der gesättigten Fettsäuren mindestens 50 Gew.-%, vorzugsweise mindestens 75 Gew.-% betragen soll. Beispiele sind Seifen aus Cocos-, Talg- und gehärteten Rübölfettsäuren gehärteten Fischölfettsäuren sowie deren Gemische. Ihr Anteil beträgt 1,0 bis 6, vorzugsweise 1,5 bis 5 und insbesondere 2 bis 4 Gew.-%.Component (b) consists of a water-soluble soap, preferably a sodium soap, which is derived from essentially saturated fatty acids with 12 to 24, preferably 14 to 22, carbon atoms, and mixtures thereof with oleic acid, the proportion of saturated fatty acids being at least 50 % By weight, preferably at least 75% by weight. Examples are soaps made from coconut oil, tallow oil and hardened rapeseed oil fatty acids, hardened fish oil fatty acids and mixtures thereof. Their proportion is 1.0 to 6, preferably 1.5 to 5 and in particular 2 to 4% by weight.

Der Bestandteil (c) besteht aus einer homopolymeren und/oder copolymeren Acrylsäure, Methacrylsäure und/oder Maleinsäure bzw. deren wasserlöslichen Salze, z.B. Natrium- oder Kaliumsalz, wobei die Natriumsalze bevorzugt sind. Geeignete Homopolymere sind Polyacrylsäure, Polymethacrylsäure und Polymaleinsäure. Geeignete Copolymere sind solche der Acrylsäure mit Methacrylsäure bzw. Copolymere der Acrylsäure, Methacrylsäure oder Maleinsäure mit Vinylethern, wie Vinylmethylether bzw. Vinylethylether, ferner mit Vinylestern, wie Vinylacetat oder Vinylpropionat, Acrylamid, Methacrylamid sowie mit Ethylen, Propylen oder Styrol. In solchen copolymeren Säuren, in denen eine der Komponenten keine Säurefunktion aufweist, beträgt deren Anteil im Interesse einer ausreichenden Wasserlöslichkeit nicht mehr als 70 Molprozent, vorzugsweise weniger als 50 Molprozent. Als besonders geeignet haben sich Copolymere der Acrylsäure bzw. Methacrylsäure mit Maleinsäure erwiesen, wie sie beispielsweise in EP 25 551-B1 näher charakterisiert sind. Es handelt sich dabei um Copolymerisate, die 40 bis 90 Gew.-% Acrylsäure bzw. Methacrylsäure und 60 bis 10 Gew.-% Maleinsäure enthalten. Besonders bevorzugt sind solche Copolymere, in denen 45 bis 85 Gewichtsprozent Acrylsäure und 55 bis 15 Gew.-% Maleinsäure anwesend sind.The component (c) consists of a homopolymeric and / or copolymeric acrylic acid, methacrylic acid and / or maleic acid or their water-soluble salts, for example sodium or potassium salt, the sodium salts being preferred. Suitable homopolymers are polyacrylic acid, polymethacrylic acid and polymaleic acid. Suitable copolymers are those of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene. In those copolymeric acids in which one of the components has no acid function, the proportion thereof, in the interest of sufficient water solubility, is not more than 70 mole percent, preferably less than 50 mole percent. Copolymers of acrylic acid or methacrylic acid with maleic acid, as described in more detail in EP 25 551-B1, have proven to be particularly suitable. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.

Das Molekulargewicht der Homo- bzw. Copolymeren beträgt im allgemeinen 2 000 bis 150 000, vorzugsweise 5 000 bis 100 000. Ihr Anteil an dem Adsorptionsmittel beträgt 1 bis 12 Gew.-%, vorzugsweise 1,5 bis 8 Gew.-% und insbesondere 2 bis 5 Gew.-%, berechnet als Natriumsalz. Mit steigendem Anteil an Polysäure bzw. deren Salzen nimmt die Beständigkeit der Körner gegen Abrieb zu. Bei einem Anteil ab 1,5 Gew.-% wird bereits eine für viele Fälle hinreichende Abriebfestigkeit erzielt. Optimale Abriebeigenschaften weisen Gemische mit 2 bis 5 Gew.-% an Natriumsalz der Polysäure auf.The molecular weight of the homo- or copolymers is generally 2,000 to 150,000, preferably 5,000 to 100,000. Their proportion of the adsorbent is 1 to 12% by weight, preferably 1.5 to 8% by weight and in particular 2 to 5% by weight, calculated as the sodium salt. The resistance of the grains to abrasion increases with an increasing proportion of polyacid or its salts. With a proportion from 1.5% by weight, sufficient abrasion resistance is achieved in many cases. Mixtures with 2 to 5% by weight of sodium salt of polyacid have optimal abrasion properties.

Es hat sich als vorteilhaft erwiesen, wenn das Gewichtsverhältnis von Seife (b) zu Polymersäure-Na-Salz (c) im Bereich von 2,5 : 1 bis 1 : 5, insbesondere im Bereich 1,5 : 1 bis 1 : 4 liegt. Diese Bereiche zeichnen sich durch gute Einspülergebnisse aus. Stärkere Abweichungen, insbesondere höhere Seifengehalte auf Kosten des Polymersäure-Anteils, führen zu ungünstigeren Werten.It has proven to be advantageous if the weight ratio of soap (b) to polymeric acid sodium salt (c) is in the range from 2.5: 1 to 1: 5, in particular in the range from 1.5: 1 to 1: 4 . These areas are characterized by good induction results. Stronger Deviations, especially higher soap contents at the expense of the polymer acid content, lead to less favorable values.

Das Natriumsulfat (Bestandteil d) liegt, als wasserfreie Substanz gerechnet, in Anteilen von 0 bis 25 Gew.-%, vorzugsweise von 0,5 bis 22 und insbesondere von 3 bis 20 Gew.-% vor. Das Natriumsulfat kann in vielen Fällen zu einer erheblichen Verbesserung der Kornstruktur und des Einspülverhaltens der Mittel beitragen und erhöht gleichzeitig deren Schüttgewicht, wodurch sich die Möglichkeit ergibt, Verpackungs- und Transportvolumen einzusparen.The sodium sulfate (component d), calculated as an anhydrous substance, is present in proportions from 0 to 25% by weight, preferably from 0.5 to 22 and in particular from 3 to 20% by weight. In many cases, the sodium sulfate can contribute to a considerable improvement in the grain structure and the flushing behavior of the agents and at the same time increases their bulk density, which makes it possible to save packaging and transport volume.

Als fakultativen Bestandteil (e) kann das Adsorptionsmittel nichtionische Tenside in Anteilen bis zu 5 Gew.-%, vorzugsweise 0 bis 4 Gew.-%, und insbesondere 0,3 bis 3 Gew.-% enthalten. Geeignete nichtionische Tenside sind insbesondere Ethoxylierungsprodukte von linearen oder methylverzweigten (Oxo-Rest) Alkoholen mit 12 bis 18 Kohlenstoffatomen und 3 bis 10 Ethylenglykolethergruppen. Brauchbar sind ferner Ethoxylierungsprodukte von vicinalen Diolen, Aminen, Thioalkoholen und Fettsäureamiden, die hinsichtlich der Anzahl der C-Atome im hydrophoben Rest und der Glykolethergruppen den beschriebenen Fettalkoholethoxylaten entsprechen. Weiterhin sind Alkylphenolpolyglykolether mit 5 bis 12 C-Atomen im Alkylrest und 3 bis 10 Ethylenglykolethergruppen brauchbar. Schließlich kommen auch Blockpolymere aus Ethylenoxid und Propylenoxid, die unter der Bezeichnung Pluronics handelsüblich sind, in Betracht. Die nichtionischen Tenside können dann anwesend sein, wenn bei der Herstellung der körnigen Adsorptionsmittel von wäßrigen Zeolith-Dispersionen ausgegangen wird, in denen diese Tenside als Dispersionsstabilisatoren fungieren. In einzelnen Fällen können die nichtionischen Tenside auch ganz oder teilweise durch andere Dispersionsstabilisatoren ersetzt sein, wie sie in DE-A-25 27 388 (US-A-4 072 622) beschrieben sind.As an optional component (e), the adsorbent can contain nonionic surfactants in proportions of up to 5% by weight, preferably 0 to 4% by weight, and in particular 0.3 to 3% by weight. Suitable nonionic surfactants are, in particular, ethoxylation products of linear or methyl-branched (oxo radical) alcohols with 12 to 18 carbon atoms and 3 to 10 ethylene glycol ether groups. Also useful are ethoxylation products of vicinal diols, amines, thioalcohols and fatty acid amides, which correspond to the fatty alcohol ethoxylates described with regard to the number of carbon atoms in the hydrophobic radical and the glycol ether groups. Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups can also be used. Finally, block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics, are also suitable. The nonionic surfactants can then be present if aqueous zeolite dispersions in which these surfactants function as dispersion stabilizers are used in the production of the granular adsorbents. In individual cases, the nonionic surfactants can also be completely or partially replaced by other dispersion stabilizers, as described in DE-A-25 27 388 (US-A-4 072 622).

10 bis 24 Gew.-% des Adsorptionsmittels entfällt auf Wasser, das in gebundener Form und als Feuchtigkeit vorliegt, wobei die Hauptmenge an den Zeolith gebunden ist. Ein Anteil des Wassers, der etwa 8 bis 18 Gew.-% (bezogen auf das Mittel) beträgt, ist bei einer Trocknungstemperatur von 145 °C entfernbar. Ein weiterer Anteil, der je nach Zeolith-Anteil zwischen 4 und 8 Gew.-% beträgt, wird bei Glühtemperatur (800 °C) frei und entspricht dem in das Kristallgitter des Zeoliths eingelagerten Wasser.10 to 24% by weight of the adsorbent is accounted for by water, which is present in bound form and as moisture, the major amount being bound to the zeolite. A proportion of the water, which is about 8 to 18 wt .-% (based on the agent), can be removed at a drying temperature of 145 ° C. Another portion, which is between 4 and 8% by weight depending on the zeolite portion, is released at the annealing temperature (800 ° C.) and corresponds to the water stored in the crystal lattice of the zeolite.

Die mittlere Korngröße des Adsorptionsmittels beträgt 0,2 bis 1,2 mm, wobei der Anteil der Körner unterhalb 0,05 mm weniger als 1 Gew.-%, vorzugsweise weniger als 0,5 Gew.-% und oberhalb 2 mm nicht mehr als 5 Gew.-% beträgt. Vorzugsweise weisen mindestens 80 Gew.-%, insbesondere mindestens 90 Gew.-% der Körner eine Größe von 0,1 bis 1,2 mm auf, wobei der Anteil der Körner zwischen 0,1 und 0,05 mm vorzugsweise nicht mehr als 3 Gew.%, insbesondere weniger als 1 Gew.-%, der Anteil der Körner zwischen 0,1 und 0,2 um weniger als 20 Gew.-%, insbesondere weniger als 10 Gew.-% und der Anteil der Körner zwischen 1,2 und 2 mm nicht mehr als 10 Gew.-%, insbesondere nicht mehr als 5 Gew.-% beträgt.The average grain size of the adsorbent is 0.2 to 1.2 mm, the proportion of the grains being less than 0.05 mm less than 1% by weight, preferably less than 0.5% by weight and not more than 2 mm Is 5% by weight. Preferably, at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.1 to 1.2 mm, the proportion of the grains between 0.1 and 0.05 mm preferably not more than 3 % By weight, in particular less than 1% by weight, the proportion of the grains between 0.1 and 0.2 by less than 20% by weight, in particular less than 10% by weight and the proportion of the grains between 1, 2 and 2 mm is not more than 10% by weight, in particular not more than 5% by weight.

Das Schüttgewicht des Adsorptionsmittels beträgt 350 bis 680 g/l, vorzugsweise 400 bis 650 g/l. Das Mittels besteht im wesentlichen aus abgerundeten Körnern, die ein sehr gutes Rieselverhalten aufweisen. Dieses sehr gute Rieselverhalten ist auch dann noch gegeben, wenn die Körner mit großen Anteilen an flüssigen bzw. halbflüssigen Waschmittelbestandteilen, insbesondere an nichtionischen Tensiden, imprägniert sind. Der Anteil dieser adsorbierten Bestandteile kann 10 bis 35 Gew.-%, bevorzugt 15 bis 30 Gew.-% bezogen auf das Adsorbat betragen.The bulk density of the adsorbent is 350 to 680 g / l, preferably 400 to 650 g / l. The agent essentially consists of rounded grains, which have a very good flow behavior. This very good flow behavior is still present when the grains are impregnated with large proportions of liquid or semi-liquid detergent components, especially nonionic surfactants. The proportion of these adsorbed components can be 10 to 35% by weight, preferably 15 to 30% by weight, based on the adsorbate.

Gegenstand der Erfindung ist ferner ein Verfahren zur Herstellung des erfindungsgemäßen körnigen Adsorptionsmittels. Dieses Verfahren ist dadurch gekennzeichnet, daß man einen wäßrigen Ansatz, enthaltend die Bestandteile (a) bis (c) sowie gegebenenfalls die Bestandteile (d), (e) und zusätzliches Alkalihydroxid, mit insgesamt 40 bis 55 Gew.-% an wasserfrei gerechneten Inhaltsstoffen mittels Düsen in einen Fallraum versprüht und mittels Trocknungsgasen, die eine Eingangstemperatur von 150 bis 280 °C und eine Austrittstemperatur von 50 bis 120 °C aufweisen, auf einen bei 145 °C entfernbaren Feuchtigkeitsgehalt von 8 bis 18 Gew.-% trocknet.The invention further relates to a method for producing the granular adsorbent according to the invention. This The process is characterized in that an aqueous mixture comprising the components (a) to (c) and, if appropriate, the components (d), (e) and additional alkali metal hydroxide, with a total of 40 to 55% by weight of anhydrously calculated ingredients Sprayed nozzles into a drop room and dried to a moisture content of 8 to 18% by weight that can be removed at 145 ° C. by means of drying gases which have an inlet temperature of 150 to 280 ° C. and an outlet temperature of 50 to 120 ° C.

Der wäßrige Ansatz kann durch Mischen der trockenen oder wasserhaltigen Bestandteile unter Zusatz des für eine Verflüssigung erforderlichen Wassers hergestellt werden. Der Zeolith kann als sprühgetrocknetes Pulver oder Granulat oder auch als wasserhaltiger Filterkuchen bzw. als wäßrige Dispersion eingesetzt werden. Sofern sprühgetrocknete Zeolithgranulate als Ausgangsmaterial verwendet werden, können diese bereits Polymere und/oder das Natriumsulfat bzw. einen Anteil davon enthalten. Anstelle der Seife bzw. der Salze der polymeren Carbonsäuren können auch die entsprechenden freien Säuren eingearbeitet und das zur Salzbildung erforderliche Alkali gesondert zugesetzt werden. Ein Zusatz von Alkalihydroxid, insbesondere NaOH, ist außerdem empfehlenswert, um die wäßrige Zeolith-Suspension bzw. den Slurry alkalisch, d. h. auf einen pH-Wert von wenigstens 8 einzustellen und einen hinreichenden Alkaliüberschuß bereitzustellen, damit während der Sprühtrocknung der pH-Wert nicht auf weniger als 8 absinkt. Eine solche pH-Wert-Erniedrigung, die zu einem Aktivitätsverlust des Zeoliths führen würde, kann durch CO₂ im Trockengas bewirkt werden. Der Zusatz von NaOH, der eine ausreichende Alkalireserve sicherstellt, kann beispielsweise bis zu 3 Gew.-% betragen. Im allgemeinen kommt man mit 0,2 bis 1 Gew.-% aus.The aqueous batch can be prepared by mixing the dry or water-containing constituents with the addition of the water required for liquefaction. The zeolite can be used as a spray-dried powder or granulate or as a water-containing filter cake or as an aqueous dispersion. If spray-dried zeolite granules are used as the starting material, these may already contain polymers and / or the sodium sulfate or a proportion thereof. Instead of the soap or the salts of the polymeric carboxylic acids, the corresponding free acids can also be incorporated and the alkali required for salt formation can be added separately. The addition of alkali hydroxide, in particular NaOH, is also recommended in order to make the aqueous zeolite suspension or the slurry alkaline, ie to a pH of at least 8 and to provide a sufficient excess of alkali so that the pH does not rise during spray drying drops less than 8. Such a pH reduction, which would lead to a loss of activity of the zeolite, can be caused by CO₂ in the dry gas. The addition of NaOH, which ensures a sufficient reserve of alkali, can be, for example, up to 3% by weight. In general, 0.2 to 1% by weight is sufficient.

Vorzugsweise beträgt der Gehalt des wäßrigen Ansatzes an wasserfreien Inhaltsstoffen 43 bis 50 Gew.-%. Seine Temperatur beträgt zweckmäßigerweise 50 bis 100 °C und seine Viskosität 2 000 bis 20 000 mPa·s, meist von 8 000 bis 14 000 mPa·s. Der Zerstäubungsdruck liegt meist bei 20 bis 120 bar, vorzugsweise 30 bis 80 bar. Das Trocknungsgas, das im allgemeinen durch Verbrennen von Heizgas oder Heizöl erhalten wird, wird vorzugsweise im Gegenstrom geführt. Bei Verwendung sogenannter Trockentürme, in welche der wäßrige Ansatz im oberen Teil über mehrere Hochdruckdüsen eingesprüht wird, beträgt die Eingangstemperatur, gemessen im Ringkanal (d. h. unmittelbar vor Eintritt in den unteren Teil des Turmes) 150 bis 280 °C, vorzugsweise 170 bis 250 °C. Das den Turm verlassende, mit Feuchtigkeit beladene Abgas weist üblicherweise eine Temperatur von 50 bis 130 °C, vorzugsweise 55 bis 115 °C auf.The content of anhydrous ingredients in the aqueous mixture is preferably 43 to 50% by weight. Its temperature is advantageously 50 to 100 ° C and its viscosity 2,000 to 20,000 mPa · s, usually from 8,000 to 14,000 mPa · s. The atomization pressure is usually 20 to 120 bar, preferably 30 to 80 bar. The drying gas, which is generally obtained by burning heating gas or heating oil, is preferably conducted in countercurrent. When using so-called drying towers, into which the aqueous batch is sprayed in the upper part via several high-pressure nozzles, the inlet temperature, measured in the ring channel (ie immediately before entering the lower part of the tower), is 150 to 280 ° C, preferably 170 to 250 ° C . The exhaust gas laden with moisture leaving the tower usually has a temperature of 50 to 130 ° C., preferably 55 to 115 ° C.

Sofern das Adsorptionsmittel mit nichtionischen Tensiden imprägniert werden soll, können diese sowohl auf das noch warme als auch auf das bereits abgekühlte bzw. nach dem Abkühlen wieder erwärmte Sprühprodukt aufgesprüht werden. Ein Erwärmen des nichtionischen Tensids auf Temperaturen zwischen 35 und 60 °C, vorzugsweise 40 bis 50 °C, beschleunigt den Adsorptionsvorgang. Die Abriebfestigkeit und Formkonstanz der Körner ist bei Einhaltung der angegebenen Mengenverhältnisse bzw. Herstellungsbedingungen so hoch, daß auch die frisch zubereiteten, insbesondere aber die abgekühlten und gegebenenfalls wieder erwärmten, ausgereiften Körner unter den üblichen Sprühmischbedingungen mit den flüssigen Zusatzstoffen behandelt, gemischt und gefördert werden können, ohne daß es zur Bildung von Feinanteilen oder gröberen Agglomeraten kommt.If the adsorbent is to be impregnated with nonionic surfactants, these can be sprayed onto the spray product which is still warm or onto the spray product which has already cooled or which has been heated again after cooling. Heating the nonionic surfactant to temperatures between 35 and 60 ° C, preferably 40 to 50 ° C, accelerates the adsorption process. The abrasion resistance and constancy of shape of the grains is so high if the specified proportions or manufacturing conditions are observed that even the freshly prepared, but especially the cooled and, if necessary, reheated, matured grains are treated, mixed and conveyed with the liquid additives under the usual spray mixing conditions can be made without the formation of fine fractions or coarser agglomerates.

Nach dem Aufbringen des flüssigen Zusatzstoffes können die Körner gegebenenfalls noch mit feinteiligen Pulvern bestäubt bzw. oberflächlich beschichtet werden. Hierdurch kann die Rieselfähigkeit noch weiter verbessert und das Schüttgewicht geringfügig erhöht werden. Geeignete Puderungsmittel weisen eine Korngröße von 0,001 bis höchstens 0,1 mm, vorzugsweise von weniger als 0,05 mm auf und können in Anteilen von 0,03 bis 3, vorzugsweise 0,05 bis 2 Gew.-%, bezogen auf das mit Zusatzstoff beladene Adsorptionsmittel angewendet werden. In Frage kommen z. B. feinpulvrige Zeolithe, Kieselsäureaerogel (Aerosil (R)), farblose oder farbige Pigmente, wie Titandioxid sowie andere, bereits zum Pudern von Körnern bzw. Waschmittelteilchen vorgeschlagene Pulvermaterialien, wie feinpulvriges Natriumtripolyphosphat, Natriumsulfat, Magnesiumsilikat und Carboxylmethylcellulose. Bei den erfindungsgemäßen Produkten ist eine solche Behandlung im allgemeinen nicht erforderlich, zumal die Einspülbarkeit dadurch nicht verbessert wird.After the liquid additive has been applied, the grains can optionally be dusted with finely divided powders or coated on the surface. As a result, the pourability can be improved even further and the bulk density can be increased slightly. Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be present in proportions of 0.03 to 3, preferably 0.05 to 2% by weight, based on that with the additive loaded adsorbents are used. For example, B. finely powdered zeolites, silica airgel (Aerosil (R) ), colorless or colored pigments, such as titanium dioxide and other powder materials already proposed for powdering granules or detergent particles, such as finely powdered sodium tripolyphosphate, sodium sulfate, magnesium silicate and carboxylmethyl cellulose. In the products according to the invention, such treatment is generally not necessary, especially since the ability to be washed in is not improved thereby.

Die zu adsorbierenden Zusatzstoffe können aus bekannten nichtionischen Tensiden bestehen, wie sie üblicherweise in Wasch- und Reinigungsmitteln verwendet werden. Weitere geeignete Zusatzstoffe sind organische Lösungsmittel, mit denen das Reinigungsvermögen von Wasch- und Reinigungsmitteln insbesondere gegenüber fettigen Verschmutzungen verbessert wird und die auf diese Weise einem körnigen Reinigungsmittel problemlos einverleibt werden können. Aber auch empfindliche Stoffe, wie Enzyme, Biocide, Duftstoffe, Bleichaktivatoren, Avivagemittel, optische Aufheller sowie anionische oder kationische Tenside können nach vorherigem Lösen bzw. Dispergieren in organischen Lösungsmitteln bzw. den flüssigen oder geschmolzenen nichtionischen Tensiden den Adsorptionsmitteln zugemischt werden. Diese Stoffe dringen zusammen mit dem Lösungs- bzw. Dispergiermittel in das poröse Korn ein und sind auf diese Weise gegen Wechselwirkungen mit anderen Pulverbestandteilen geschützt.The additives to be adsorbed can consist of known nonionic surfactants, as are usually used in washing and cleaning agents. Other suitable additives are organic solvents, with which the cleaning ability of detergents and cleaning agents is improved, in particular with regard to greasy soiling, and which can be incorporated into a granular cleaning agent without problems in this way. However, even sensitive substances such as enzymes, biocides, fragrances, bleach activators, softening agents, optical brighteners and anionic or cationic surfactants can be added to the adsorbents after they have been dissolved or dispersed in organic solvents or the liquid or melted nonionic surfactants. These substances come together with the solvent or dispersant in the porous grain and are thus protected against interactions with other powder components.

Bevorzugte Waschmittelbestandteile, die an dem Adsorptionsmittel gebunden sind und mit diesem zusammen als rieselfähiges Gemisch vorliegen, sind flüssige bis pastöse nichtionische Tenside aus der Klasse der Polyglykolether, abgeleitet von Alkoholen mit 10 bis 22, insbesondere 12 bis 18 C-Atomen. Diese Alkohole können gesättigt oder olefinisch ungesättigt, linear oder in 2-Stellung methylverzweigt (Oxo-Rest) sein. Ihre Umsetzungsprodukte mit Ethylenoxid (EO) bzw. Propylenoxid (PO) sind wasserlöslich bzw. in Wasser dispergierbare Gemische von Verbindungen mit unterschiedlichem Alkoxylierungsgrad. Die Zahl der EO- bzw. PO-Gruppen entspricht bei technischen Alkoxylaten dem statistischen Mittelwert.Preferred detergent constituents which are bound to the adsorbent and are present together with this as a free-flowing mixture are liquid to pasty nonionic surfactants from the class of the polyglycol ethers, derived from alcohols having 10 to 22, in particular 12 to 18, carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical). Their reaction products with ethylene oxide (EO) or propylene oxide (PO) are water-soluble or water-dispersible mixtures of compounds with different degrees of alkoxylation. The number of EO or PO groups corresponds to the statistical mean for technical alkoxylates.

Beispiele für geeignete ethoxylierte Fettalkohole sind C₁₂₋₁₈-Cocosalkohole mit 3 bis 12 EO, C₁₆₋₁₈-Talgalkohol mit 4 bis 16 EO, Oleylalkohol mit 4 bis 12 EO sowie aus anderen nativen Fettalkoholgemischen erhältliche Ethoxylierungsprodukte entsprechender Ketten- und EO-Verteilung. Aus der Reihe der ethoxylierten Oxoalkohole sind beispielsweise solche der Zusammensetzung C₁₂₋₁₅ + 5 bis 10 EO und C₁₄-C₁₅ + 6 bis 12 EO geeignet. Durch eine erhöhte Waschkraft sowohl gegenüber fettartigen und mineralischen Anschmutzungen zeichnen sich Gemische aus niedrig und hoch ethoxylierten Alkoholen aus, beispielsweise solche aus Talgalkohol + 3 bis 6 EO und Talgalkohol + 12 bis 16 EO oder C₁₃₋₁₅Oxoalkohol + 3 bis 5 EO und C₁₂₋₁₄-Oxoalkohol + 8 bis 12 EO. Besonders günstige Einspüleigenschaften haben Mittel, in denen die adsorbierten nichtionischen Tenside sowohl lange hydrophobe Reste als auch höhere Ethoxylierungsgrade aufweisen.Examples of suitable ethoxylated fatty alcohols are C₁₂₋₁₈ coconut alcohols with 3 to 12 EO, C₁₆₋₁₈ tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures. From the series of ethoxylated oxo alcohols, for example, those of the composition C₁₂₋₁₅ + 5 to 10 EO and C₁₄-C₁₅ + 6 to 12 EO are suitable. Mixtures of low and highly ethoxylated alcohols are distinguished by an increased detergency against both greasy and mineral soiling, for example those from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or C₁₃₋₁₅Oxoalcohol + 3 to 5 EO and C₁₂₋₁₄ -Oxo alcohol + 8 to 12 EO. Agents in which the adsorbed nonionic surfactants have both long hydrophobic residues and higher degrees of ethoxylation have particularly favorable flushing properties.

Überraschenderweise hat sich gezeigt, daß sich die Löslichkeitseigenschaften und das Einspülverhalten der mit nichtionischen Tensiden imprägnierten Adsorptionsmittel noch weiter steigern läßt, wenn die nichtionischen Tenside zusätzlich eine in Wasser schwer oder nicht lösliche, wohl aber dispergierbare, polare, hydrophobe Reste aufweisende Verbindung enthalten. Beispiele hierfür sind freie, seifenbildende Fettsäuren. Partialester von mehrwertigen Alkoholen, wie Partialglyceride und Fettsäureglykolester, Fettsäureamide, Fettsäurepartialamide von Alkylendiaminen und Hydroxyalkyl-alkylendiaminen, Fettamine, quartäre Ammoniumbasen bzw. deren Salze, Fettalkohole sowie schwerlösliche anionische Tenside, wie die Di-salze von Alphasulfofettsäuren. Auch Gemische derartiger schwer löslicher bzw. unlöslicher Verbindungen können eingesetzt werden. Die Anzahl der C-Atome soll in den hydrophoben Resten mindestens 10, üblicherweise 12 bis 18 betragen. Die Mengenverhältnisse von nichtionischem Tensid zu schwer löslicher Zusatzverbindung beträgt 99 : 1 bis 70 : 30. Wesentlich für den Erfolg ist, daß nichtionisches Tensid und Zusatzstoff zuvor miteinander vermischt werden. Ein aufeinanderfolgendes Aufbringen der Einzelstoffe auf das Adsorptionsmittel führt nicht zu einer Verbesserung des Löslichkeits- und Einspülverhaltens.Surprisingly, it has been found that the solubility properties and the flushing-in behavior of the adsorbents impregnated with nonionic surfactants can be increased even further if the nonionic surfactants additionally contain a compound which is difficult or not soluble in water, but does have a dispersible polar, hydrophobic radical. Examples of this are free, soap-forming fatty acids. Partial esters of polyhydric alcohols, such as partial glycerides and fatty acid glycol esters, fatty acid amides, fatty acid partial amides of alkylenediamines and hydroxyalkylalkylenediamines, fatty amines, quaternary ammonium bases or their salts, fatty alcohols and poorly soluble anionic surfactants, such as the di-salts of alphasulfo fatty acids. Mixtures of such poorly soluble or insoluble compounds can also be used. The number of carbon atoms in the hydrophobic radicals should be at least 10, usually 12 to 18. The quantitative ratios of nonionic surfactant to sparingly soluble additional compound is 99: 1 to 70:30. It is essential for the success that the nonionic surfactant and additive are mixed together beforehand. A successive application of the individual substances to the adsorbent does not lead to an improvement in the solubility and flushing behavior.

Bevorzugte Beispiele dieser Gruppe sind Cocos-, Talg- und Rübölfettsäuren, die auch gehärtet sein können, Gemische aus Talgfettsäurepartialglycerid und dem Talgfettsäurepartialamid des Hydroxyethyl-ethylendiamins, Di-talgalkyl-dimethyl-ammonium-chlorid und das Di-natriumsalz von Alphasulfofettsäuren, abgeleitet von gehärteten C₁₂₋₁₈-Fettsäuren.Preferred examples of this group are coconut oil, tallow and rapeseed oil fatty acids, which can also be hardened, mixtures of tallow fatty acid partial glyceride and the tallow fatty acid partial amide of hydroxyethyl-ethylenediamine, di-tallow-alkyl-dimethyl-ammonium chloride and the disodium salt of alpha-sulfo fatty acids derived from hardened C₁₂₋₁₈ fatty acids.

Die mit den nichtionischen Tensiden bzw. mit den Gemischen aus nichtionischem Tensid und Zusatzstoff imprägnierten körnigen Adsorptionsmittel können mit weiteren pulverförmigen bis körnigen Waschmitteln bzw. Waschmittelkomponenten, wie sie beispielweise durch Sprühtrocknung oder Granulation erhältlich sind, oder auch mit Bleichmitteln bzw. mit bleichmittelhaltigen Waschmitteln bekannter Zusammensetzung in jedem beliebigen Verhältnis vermischt werden. Hierbei ist ihre gute Rieselfähigkeit sowie ihre hohe Kornstabilität von großem Vorteil, da eine unerwünschte Bildung von Abrieb und Staub vermieden wird. Die Pulvergemische sind ihrerseits lagerbeständig und neigen nicht zum Verklumpen oder Ausschwitzen des nichtionischen Tensids. Bei der Anwendung sind sie im Vergleich zu bekannten Mitteln besonders gut einspülbar.The granular adsorbents impregnated with the nonionic surfactants or with the mixtures of nonionic surfactant and additive can be mixed with further powdery to granular detergents or detergent components, such as, for example are obtainable by spray drying or granulation, or can also be mixed with bleaches or with bleach-containing detergents of known composition in any ratio. Here, their good flowability and their high grain stability are of great advantage, since an undesirable formation of abrasion and dust is avoided. The powder mixtures are in turn stable in storage and do not tend to clump or exude the nonionic surfactant. When used, they are particularly easy to flush in compared to known agents.

Beispiele 1 bis 4Examples 1 to 4

In einem mit Rührvorrichtung ausgerüsteten Ansatzbehälter wurden die folgenden Bestandteile und Zusatz von Wasser zu einem Slurry vermischt (GT = Gewichtsteile)

  • a) 67,3 GT Zeolith NaA (wasserfrei gerechnet) enthaltend
    0,4 GT freies NaOH
  • b) 4,0 GT Acrylsäure-Maleinsäure Copolymer (Na-Salz)
  • c) 2,5 GT Na-Seife (C₁₂₋₁₈-Cocos-Talgseife 1:1)
  • d) 4,5 GT Natriumsulfat
  • e) 2,1 GT ethoxylierter Talg-Fettalkohol mit 5 EO
Der verwendete Zeolith hatte ein Calciumbindevermögen von 165 mg CaO/g und eine mittlere Partikelgröße von 3 µm, wobei keine Anteile über 20 µm vorlagen. Eingesetzt wurde er als wäßrige Dispersion, enthaltend 48 Gew.-% wasserfreien Zeolith, 1,5 Gew.-% der Komponente (e) und 53,1 Gew.-% Wasser. Als Polycarbonsäure wurde ein Copolymerisat aus Acrylsäure und Maleinsäure mit einem Molekulargewicht von 70 000 (Sokalan(R)) in Form des Natriumsalzes zum Einsatz gebracht.The following constituents and addition of water were mixed to form a slurry in a batch container equipped with a stirring device (GT = parts by weight)
  • a) containing 67.3 pbw of zeolite NaA (calculated as anhydrous)
    0.4 GT free NaOH
  • b) 4.0 pbw of acrylic acid-maleic acid copolymer (Na salt)
  • c) 2.5 GT Na soap (C₁₂₋₁₈ coconut tallow soap 1: 1)
  • d) 4.5 pbw of sodium sulfate
  • e) 2.1 pbw of ethoxylated tallow fatty alcohol with 5 EO
The zeolite used had a calcium binding capacity of 165 mg CaO / g and an average particle size of 3 μm, with no proportions above 20 μm. It was used as an aqueous dispersion containing 48% by weight of anhydrous zeolite, 1.5% by weight of component (s) and 53.1% by weight of water. A copolymer of acrylic acid and maleic acid with a molecular weight of 70,000 (Sokalan (R) ) in the form of the sodium salt was used as the polycarboxylic acid.

Die eine Temperatur von 85 °C und eine Viskosität von 10 200 mPa·s aufweisende Aufschlämmung wurde mit einem Druck von 40 AT in einem Turm versprüht, in dem Verbrennungsgase mit einer Temperatur von 226 °C (gemessen im Ringkanal) dem Sprühprodukt entgegengeführt wurden. Die Austrittstemperatur des Trockengases betrug 60 °C. Das den Sprühturm verlassende körnige Adsorptionsmittel enthielt

  • f) 19,2 GT Wasser
Das durch Siebanalyse ermittelte Kornspektrum ergab die folgende Gewichtsverteilung: mm über 1,6 bis 0,8 bis 0,4 bis 0,2 bis 0,1 unter 0,1 Gew.-% 0 2 39 52 7 0 The slurry, which had a temperature of 85 ° C. and a viscosity of 10 200 mPa · s, was sprayed at a pressure of 40 AT in a tower in which combustion gases at a temperature of 226 ° C. (measured in the ring channel) were directed towards the spray product. The outlet temperature of the dry gas was 60 ° C. The granular adsorbent leaving the spray tower contained
  • f) 19.2 pbw of water
The grain spectrum determined by sieve analysis gave the following weight distribution: mm over 1.6 to 0.8 to 0.4 up to 0.2 to 0.1 less than 0.1 % By weight 0 2nd 39 52 7 0

Das Litergewicht betrug 563 g/l.The liter weight was 563 g / l.

Die Körner wurden in einer Sprühmischapparatur, bestehend aus einem horizontal angeordneten, mit Misch- und Förderorganen und Sprühdüsen ausgerüsteten zylindrischen Trommel (LÖDIGE-Mischer) mit auf ca. 50 °C erwärmten nichtionischen Tensiden bzw. Tensidgemischen besprüht. Die Temperatur des Adsorptionsmittels betrug 20 °C. Die Tensidschmelze bestand aus (bezogen auf das Endgewicht des imprägnierten Granulats):

  • 1) 18,0 Gew.-% Talgalkohol + 5 EO
  • 2) 15,5 Gew.-% 1 : 4 - Gemisch aus Cocosalkohol + 3 EO und Talgalkohol + 5EO
  • 3) 15,2 Gew.-% Ethoxylat gemäß (2) und
    0,3 Gew.-% hydrierte Talgfettsäure
  • 4) 15,2 Gew.-% Ethoxylat gemäß (2) und
    0,3 Gew.-% eines 1:1 Gemisches aus
    Talgfettsäurepartialglycerid und Talgfettsäureamid des Hydroxylethyl-ethylendiamins.
The grains were sprayed in a spray mixing apparatus consisting of a horizontally arranged cylindrical drum equipped with mixing and conveying elements and spray nozzles (LÖDIGE mixer) with nonionic surfactants or surfactant mixtures heated to about 50 ° C. The temperature of the adsorbent was 20 ° C. The surfactant melt consisted of (based on the final weight of the impregnated granulate):
  • 1) 18.0% by weight tallow alcohol + 5 EO
  • 2) 15.5% by weight 1: 4 - mixture of coconut alcohol + 3 EO and tallow alcohol + 5EO
  • 3) 15.2% by weight of ethoxylate according to (2) and
    0.3% by weight hydrogenated tallow fatty acid
  • 4) 15.2% by weight of ethoxylate according to (2) and
    0.3% by weight of a 1: 1 mixture
    Tallow fatty acid partial glyceride and tallow fatty acid amide of hydroxylethyl-ethylenediamine.

Die Schüttgewichte der Produkte erhöhten sich durch die Imprägnierung auf Werte zwischen 650 bis 700 g/l. Zum Vergleich wurden (V1) ein körniger, sprühgetrockneter Zeolith NaA sowie (V2) ein gemäß DE-A-34 44 960 hergestelltes seifenfreies Trägermaterial verwendet und in gleicher Weise verarbeitet.The bulk weights of the products increased to values between 650 and 700 g / l due to the impregnation. For comparison, (V1) a granular, spray-dried zeolite NaA and (V2) a soap-free carrier material produced in accordance with DE-A-34 44 960 were used and processed in the same way.

Zur Bestimmung des Rieselverhaltens wurde 1 Liter des Pulvers in einem an seiner Auslauföffnung verschlossenen Trichter mit folgenden Abmessungen gefüllt. Durchmesser der oberen Öffnung 150 mm Durchmesser der unteren Öffnung 10 mm Höhe des konischen Trichterbereiches 230 mm Höhe des konischen Trichterbereiches 230 mm Höhe des unten angesetzten zylindrischen Bereichs 20 mm Neigungswinkel des konischen Bereiches 73 ° To determine the flow behavior, 1 liter of the powder was filled in a funnel closed at its outlet opening with the following dimensions. Diameter of the top opening 150 mm Diameter of the bottom opening 10 mm Height of the conical funnel area 230 mm Height of the conical funnel area 230 mm Height of the cylindrical area below 20 mm Inclination angle of the conical area 73 °

Als Vergleichssubstanz wurde trockener Seesand mit folgendem Kornspektrum gewählt. mm über 1,5 bis 0,8 bis 0,4 bis 0,2 bis 0,1 Gew.-% 0,2 11,9 54,7 30,1 3,1 Dry sea sand with the following grain spectrum was chosen as the reference substance. mm over 1.5 to 0.8 to 0.4 up to 0.2 to 0.1 % By weight 0.2 11.9 54.7 30.1 3.1

Die Auslaufzeit des trockenen Sandes nach Freigabe der Ausflußöffnung wurde mit 100 % angesetzt. Die Rieselfähigkeit der erfindungsgemäßen Produkte ist in %, bezogen auf diesen 100 %-Wert, angegeben. Werte über 75 % gelten als sehr gut.The run-off time of the dry sand after opening the outflow opening was set at 100%. The pourability of the products according to the invention is given in%, based on this 100% value. Values above 75% are considered very good.

In einer weiteren Versuchsreihe wurde das Einspülverhalten untersucht, wobei Bedingungen simuliert wurden, die einer unter kritischen Bedingungen betriebenen Einspülvorrichtung einer Haushaltswaschmaschine entsprechen. In die Versuchsvorrichtung (ZANUSSI-Einspülrinne) wurden jeweils 100 g Produkt eingegeben und nach einer Ruhezeit von 1 Minute wurden innerhalb von 90 sec. 10 Liter Leitungswasser eingespeist. Nach Einspülen von 10 Liter wurden die verbleibenden Rückstände in nassem Zustand zurückgewogen und 30 % des Gewichtes als Wasser rechnerisch abgezogen. Für das Einspülverhalten wurden folgende Bewertungen vergeben:

A =
vollständiges Einspülen (die Zahl gibt die benötigten Liter Wasser an),
B =
Rückstand weniger als 10 g (die Zahl gibt die Rückstandsmenge in g an),
C =
mehr als 10 g Rückstand (mit Angabe des Rückstandes in g).
In a further series of experiments, the washing-in behavior was investigated, conditions being simulated which correspond to a washing-in device of a household washing machine operated under critical conditions. In each case, 100 g of product were introduced into the test device (ZANUSSI induction channel) and, after a rest period of 1 minute, 10 liters of tap water were fed in within 90 seconds. After flushing in 10 liters, the remaining residues were weighed out while wet and 30% of the weight was calculated as water. The following ratings were assigned for the induction behavior:
A =
complete rinsing (the number indicates the liters of water required),
B =
Residue less than 10 g (the number indicates the amount of residue in g),
C =
more than 10 g of residue (stating the residue in g).

A- und B-Werte sind für die Praxis sehr gut bis befriedigend. C-Werte bezeichnen ein unzureichendes Einspülverhalten.A and B values are very good to satisfactory in practice. C values indicate inadequate induction behavior.

Das Adsorptionsmittel wies eine Einspülnote von A 5 auf. Zusätzlich wurden 2 Versuchsreihen durchgeführt und zwar mit dem imprägnierten Adsorptionsmittel ohne Zusatz eines Waschmittels sowie eines Gemisches aus 25 Teilen des imprägnierten Adsorptionsmittels und 75 Teilen eines Waschmittels, bestehend aus 50 Teilen Turmsprühpulver, 20 Teilen Natrium-Perborat und 5 Teilen an weiteren granularen Bestandteilen, enthaltend Entschäumer, Enzyme, Duftstoffe und Bleichaktivatoren (Bezeichnung "mit W").The adsorbent had a flushing grade of A 5. In addition, 2 series of tests were carried out, with the impregnated adsorbent without the addition of a detergent and a mixture of 25 parts of the impregnated adsorbent and 75 parts of a detergent, consisting of 50 parts of tower spray powder, 20 parts of sodium perborate and 5 parts of other granular constituents Defoamers, enzymes, fragrances and bleach activators (called "with W").

Das Turmsprühpulver wies die folgende Zusammensetzung auf (in Gew.-%):
17,6 % n-Dodecylbenzolsulfonat (Na-Salz)
2,5 % Talgseife (Na-Salz)
4,0 % Talgalkohol + 14 EO
20,5 % Zeolith NaA (wasserfrei gerechnet)
15,0 % Soda
5,0 % Copolymerisat (b)
0,5 % Na-Hydroxyethan-diphosphonat
3,0 % Natriumsilikat 1 : 3,3
1,6 % Carboxymethylcellulose
18,0 % Natriumsulfat
12,3 % Wasser
Die Ergebnisse sind in der folgenden Tabelle zusammengefaßt: Beispiel Rieselfähigkeit Einspülverhalten ohne W mit W 1 82 B 2 A 8 2 81 B 1 A 6 3 80 A 5 A 5 4 80 A 6 A 4 V1 58 C 48 C 11 V2 80 C 48 C 40 The tower spray powder had the following composition (in% by weight):
17.6% n-dodecylbenzenesulfonate (Na salt)
2.5% tallow soap (Na salt)
4.0% tallow alcohol + 14 EO
20.5% zeolite NaA (calculated anhydrous)
15.0% soda
5.0% copolymer (b)
0.5% Na hydroxyethane diphosphonate
3.0% sodium silicate 1: 3.3
1.6% carboxymethyl cellulose
18.0% sodium sulfate
12.3% water
The results are summarized in the following table: example Flowability Induction behavior without W with W 1 82 B 2 A 8 2nd 81 B 1 A 6 3rd 80 A 5 A 5 4th 80 A 6 A 4 V1 58 C 48 C 11 V2 80 C 48 C 40

Beispiel 5Example 5

In der in Beispiel 1 beschriebenen Weise wurde ein körniges Granulat folgender Zusammensetzung hergestellt (in Gew.%):

  • (a) 60,0 % Zeolith (wasserfrei gerechnet) enthaltend
    0,35 % freies NaOH
  • (b) 5,2 % Acrylsäure-Maleinsäure-Copolymer (Na-Salz)
  • (c) 2,0 % Na-Talgseife
  • (d) 13,2 % Natriumsulfat
  • (e) 1,85 % Talgfettalkohol + 5EO
  • (f) 17,4 % Wasser
Das Litergewicht betrug 590 g/l. Die Siebanalyse ergab folgende Kornverteilung: mm über 1,6 bis 0,8 bis 0,4 bis 0,2 bis 0,1 unter 0,1 Gew.-% 0 3 41 50 6 - In the manner described in Example 1, granular granules of the following composition were produced (in% by weight):
  • (a) containing 60.0% zeolite (calculated as anhydrous)
    0.35% free NaOH
  • (b) 5.2% acrylic acid-maleic acid copolymer (Na salt)
  • (c) 2.0% Na tallow soap
  • (d) 13.2% sodium sulfate
  • (e) 1.85% tallow fatty alcohol + 5EO
  • (f) 17.4% water
The liter weight was 590 g / l. The sieve analysis showed the following grain distribution: mm over 1.6 to 0.8 to 0.4 up to 0.2 to 0.1 less than 0.1 % By weight 0 3rd 41 50 6 -

Wie in Beispiel 1 beschrieben, wurden 84 GT des Adsorptionsmittels in einer Sprühmisch-Apparatur mit 16 GT eines geschmolzenen Tensidgemisches gemäß Beispiel 2 imprägniert. Das Schüttgewicht des Produktes betrug 710 g/l, das Rieselverhalten 80 % und der Einspültest A8. Ein Gemisch aus 20 GT dieses Granulates, 80 GT des in Beispiel 1 - 4 eingesetzten sprühgetrockneten Waschmittels, 15 GT an Natriumperborat und 5 GT sonstigen granularen Bestandteilen ergab unter den gleichen Versuchsbedingungen den Einspül-Testwert A6.As described in Example 1, 84 pbw of the adsorbent were impregnated in a spray mixer with 16 pbw of a molten surfactant mixture according to Example 2. The bulk weight of the product was 710 g / l, the flow behavior 80% and the wash-in test A8. A mixture of 20 pbw of these granules, 80 pbw of the spray-dried detergent used in Examples 1-4, 15 pbw of sodium perborate and 5 pbw of other granular constituents gave the induction test value A6 under the same test conditions.

Beispiel 6Example 6

Ein nach den Angaben von Beispiel 1 hergestellten granulares Adsorptionsmittel wies die folgende Zusammensetzung auf (in Gew.%):

  • (a) 60,0 % Zeolith, alkalisiert mit
    0,8 % NaOH
  • (b) 3,0 % Talg-Cocosseife 1:1 (Na-Salz)
  • (c) 2,2 % Acrylsäure-Maleinsäure-Copolymer (Na-Salz)
  • (d) 15,2 % Na-Sulfat
  • (e) 1,8 % Talalkohol + 5EO
  • (f) 17,0 % Wasser
A granular adsorbent prepared as described in Example 1 had the following composition (in% by weight):
  • (a) 60.0% zeolite, alkalized with
    0.8% NaOH
  • (b) 3.0% tallow coconut soap 1: 1 (Na salt)
  • (c) 2.2% acrylic acid-maleic acid copolymer (Na salt)
  • (d) 15.2% Na sulfate
  • (e) 1.8% talc alcohol + 5EO
  • (f) 17.0% water

Nach Absieben von Fein- und Grobanteilen wies das Produkt ein Schüttgewicht von 580 g/l bei folgender Kornverteilung auf: mm über 1,6 bis 0,8 bis 0,4 bis 0,2 bis 0,1 unter 0,1 Gew.-% 0 8 38 50 4 0 After screening fine and coarse fractions, the product had a bulk density of 580 g / l with the following particle size distribution: mm over 1.6 to 0.8 to 0.4 up to 0.2 to 0.1 less than 0.1 % By weight 0 8th 38 50 4th 0

82 Gew.% des Granulates wurden mit 18 Gew.-% eines C₁₃₋₁₅-Oxoalkoholes + 5EO imprägniert. Das Einspülverhalten des behandelten Produktes wurde mit Note B5 bewertet. Das Gemisch aus 30 GT des Produktes mit 60 GT sprühgetrocknetem Waschpulver und 10 GT Perborat-Monohydrat hatte die Einspülnote B1.82% by weight of the granules were impregnated with 18% by weight of a C₁₃₋₁₅ oxo alcohol + 5EO. The wash-in behavior of the treated product was rated B5. The mixture of 30 pbw of the product with 60 pbw of spray-dried washing powder and 10 pbw of perborate monohydrate had the wash-in grade B1.

Beispiel 7Example 7

Es wurde ein wäßriger Slurry unter Verwendung eines sprühgetrockneten Zeolith-Granulates zubereitet. Dieses Granulat bestand aus einem Gemisch von Zeolith (mit einem bei Glühtemperatur entfernbaren Wassergehalt von 20 Gew.-%) sowie aus wasserfreiem Natriumsulfat. Dem Slurry wurde weiterhin Na-Polyacrylat (MG 32 000), Cocos-Talgseife und Natriumhydroxyd zugemischt. Der Wassergehalt des Slurry betrug 52,5 Gew.-% (einschließlich des an den Zeolith gebundenen Wassers). Der eine Temperatur von 88 °C aufweisende Slurry wurde im Sprühturm nach dem Gegenstromverfahren sprühgetrocknet, wobei die Trockengase eine Eingangstemperatur von 130 °C und eine Ausgangstemperatur von 67 °C aufwiesen. Das Granulat wies die folgende Zusammensetzung auf (in Gew.-%):
59,0 % Zeolith (wasserfrei)
0,6 % NaOH
2,4 % Seife
2,5 % Na-Polyacrylat
18,0 % Natriumsulfat
17,5 % Wasser
Korngröße 1,2 bis 0,1 mm, mittlere Korngröße 0,3 g/l, Schüttgewicht 600 g/l. Nach dem Imprägnieren mit 16 Gew.-% (bezogen auf Imprägnat) mit einem Fettalkoholethoxylat-Gemisch gemäß Beispiel 2 resultierte eine Einspülnote von B2 und nach dem Vermischen mit einem Waschpulver gemäß Beispiel 6 eine Einspülnote von A8.An aqueous slurry was prepared using spray dried zeolite granules. These granules consisted of a mixture of zeolite (with a removable one at annealing temperature Water content of 20% by weight) and from anhydrous sodium sulfate. Na polyacrylate (MW 32,000), coconut tallow soap and sodium hydroxide were also added to the slurry. The water content of the slurry was 52.5% by weight (including the water bound to the zeolite). The slurry, which had a temperature of 88 ° C., was spray-dried in the spray tower by the countercurrent method, the drying gases having an inlet temperature of 130 ° C. and an outlet temperature of 67 ° C. The granules had the following composition (in% by weight):
59.0% zeolite (anhydrous)
0.6% NaOH
2.4% soap
2.5% Na polyacrylate
18.0% sodium sulfate
17.5% water
Grain size 1.2 to 0.1 mm, average grain size 0.3 g / l, bulk density 600 g / l. After impregnation with 16% by weight (based on impregnate) with a fatty alcohol ethoxylate mixture according to Example 2, a wash-in grade of B2 resulted and after mixing with a washing powder according to Example 6, a wash-in grade of A8.

Claims (14)

  1. A granular adsorbent having a high adsorption capacity for liquid to pasty components of detergents and cleaning preparations and improved flushing behavior, consisting essentially of
    (a) 45 to 75% by weight (expressed as anhydrous substance) of a cation-exchanging, finely crystalline, synthetic sodium alumosilicate containing bound water of the zeolite NaA type and mixtures thereof with zeolite NaX,
    (b) 1 to 6% by weight soap derived from substantially saturated C₁₂₋₂₄ fatty acids in the form of the sodium and/or potassium soap and mixtures thereof with oleic acid, the saturated fatty acids making up at least 50% by weight,
    (c) 1 to 12% by weight of a homopolymeric or copolymeric acrylic acid, methacrylic acid and/or maleic acid and water-soluble salts thereof, expressed as sodium salt,
    (d) 0 to 25% by weight sodium sulfate,
    (e) 0 to 5% by weight of a nonionic surfactant containing polyglycol ether groups,
    (f) 10 to 24% by weight water,
    the adsorbent having an average particle size of 0.2 to 1.2 mm, the fraction with a particle size of less than 0.05 mm being less than 1% by weight, the fraction with a particle size of more than 2 mm being no more than 5% by weight and the apparent density being in the range from 350 to 680 g/l.
  2. An adsorbent as claimed in claim 1 containing 50 to 70% by weight and more particularly 55 to 68% by weight of component (a).
  3. An adsorbent as claimed in claim 1 or 2 containing 1.5 to 5% by weight and more particularly 2 to 4% by weight of component (b).
  4. An adsorbent as claimed in one or more of claims 1 to 3 containing 1.5 to 8% by weight and more particularly 2 to 5% by weight of component (c).
  5. An adsorbent as claimed in one or more of claims 1 to 4 containing 0.5 to 22% by weight and more particularly 3 to 20% by weight of component (d).
  6. An adsorbent as claimed in one or more of claims 1 to 5 containing 0 to 4% by weight and preferably 0.3 to 3% by weight of component (e).
  7. An adsorbent as claimed in one or more of claims 1 to 6, in which at least 80% by weight and more particularly at least 90% by weight of the particles are between 0.1 and 1.2 mm in size, the fraction of particles between 0.1 and 0.05 mm in size being no more than 3% by weight and, in particular, less than 1% by weight and the fraction of particles larger than 1.2 to 2 mm in size being no more than 10% by weight and, more particularly, no more than 5% by weight.
  8. An adsorbent as claimed in one or more of claims 1 to 7, in which component (b) consists of the sodium soap of C₁₄₋₂₂ fatty acids of which at least 75% by weight are saturated.
  9. An adsorbent as claimed in one or more of claims 1 to 8, in which component (c) consists of polyacrylic acid or copolymers thereof with maleic acid.
  10. An adsorbent as claimed in one or more of claims 1 to 9, characterized in that it is impregnated with 10 to 35% by weight, based on the final treated product, of at least one nonionic surfactant.
  11. A detergent as claimed in claim 10, characterized in that the nonionic surfactant is mixed with a compound containing hydrophobic residues which is insoluble or only poorly soluble in water.
  12. A process for the production of the granular adsorbent claimed in one or more of claims 1 to 9, characterized in that an aqueous slurry of components (a) to (c) and, optionally, (d) and (e), which contains 40 to 55% by weight anhydrous ingredients, is sprayed by means of nozzles into a tower and dried to a moisture content removable at 145°C of 8 to 18% by weight by means of drying gases which have an entry temperature of 150 to 280°C and an exit temperature of 50 to 120°C.
  13. A process for the production of the adsorbent impregnated with nonionic surfactants claimed in one or more of claims 1 to 12, characterized in that the spray-dried adsorbent is mixed with the liquid or molten nonionic surfactant or surfactant mixture.
  14. A powder-form to granular, phosphate-free to low-phosphate detergent, characterized by a content of the impregnated adsorbent claimed in claim 10 or 11.
EP89109494A 1988-06-03 1989-05-26 Granular adsorption material with improved flushing property Expired - Lifetime EP0344629B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89109494T ATE98294T1 (en) 1988-06-03 1989-05-26 GRANULAR ADSORPTION AGENT WITH IMPROVED Rinsing BEHAVIOR.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3818829 1988-06-03
DE3818829A DE3818829A1 (en) 1988-06-03 1988-06-03 KOENIGES ADSORPTIONSMITTEL WITH IMPROVED SPOONING BEHAVIOR

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EP0344629B1 true EP0344629B1 (en) 1993-12-08

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GB8924294D0 (en) * 1989-10-27 1989-12-13 Unilever Plc Detergent compositions
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WO1989012087A1 (en) 1989-12-14
KR960012274B1 (en) 1996-09-18
ATE98294T1 (en) 1993-12-15
JP2633045B2 (en) 1997-07-23
DK272790A (en) 1990-11-15
US5139693A (en) 1992-08-18
DE3818829A1 (en) 1989-12-14
KR900701993A (en) 1990-12-05
ES2047059T3 (en) 1994-02-16
EP0344629A1 (en) 1989-12-06
JPH03504734A (en) 1991-10-17
DE58906340D1 (en) 1994-01-20
DK272790D0 (en) 1990-11-15

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