EP0355626A1 - Method for the production of low phosphate detergent tablets - Google Patents

Method for the production of low phosphate detergent tablets Download PDF

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Publication number
EP0355626A1
EP0355626A1 EP89114911A EP89114911A EP0355626A1 EP 0355626 A1 EP0355626 A1 EP 0355626A1 EP 89114911 A EP89114911 A EP 89114911A EP 89114911 A EP89114911 A EP 89114911A EP 0355626 A1 EP0355626 A1 EP 0355626A1
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EP
European Patent Office
Prior art keywords
weight
tablet
components
nonionic surfactants
phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP89114911A
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German (de)
French (fr)
Inventor
Hans Kruse
Monika Dr. Böcker
Jochen Dr. Jacobs
Ulrich Dr. Jahnke
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0355626A1 publication Critical patent/EP0355626A1/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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry tablets
    • 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

Definitions

  • Detergent tablets have a number of advantages over powdered detergents, such as simple dosing and low packaging volume requirements. Problems arise, however, in that relatively high compression pressures have to be used to achieve adequate dimensional stability and fracture resistance when pressing the powdered raw materials. Because of the high degree of compaction, such tablets often have inadequate disintegration and dissolving properties when used, with the result that undissolved parts remain in the washing-up compartments of the washing machines. These problems already exist with phosphate-rich, i.e. H.
  • TPP tripolyphosphate
  • the weight ratio of anionic surfactant to nonionic surfactant in component (A) should preferably not be less than a ratio of 10: 1.
  • Phosphate-reduced in the context of the invention is to be understood as meaning those compositions which contain less than 10% by weight, preferably less than 5% by weight and in particular less than 1% by weight of phosphate, calculated as anhydrous pentasodium triphosphate.
  • the agents are phosphate-free.
  • compositions contain fine crystalline zeolite as a phosphate substitute in amounts of 10 to 40% by weight, preferably 20 to 35% by weight.
  • Suitable zeolites are those 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 ⁇ m and consist of at least 80% particles smaller than 10 ⁇ m. Their average particle size (volume distribution, measurement method: Coulter Counter) is 1 to 10 ⁇ m.
  • Their calcium binding capacity which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g.
  • Examples of homopolymeric and / or copolymeric carboxylic acids or their water-soluble salts, of which the sodium salts are preferably used, are polyacrylic acid, polymethacrylic acid and polymaleic acid, copolymers of acrylic acid with methacrylic acid or copolymers of 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.
  • the proportion thereof, in the interest of sufficient water solubility is not more than 50 mole percent, preferably less than 30 mole percent.
  • Copolymers of acrylic acid have proven particularly suitable or methacrylic acid with maleic acid, as described in more detail, for example, in EP 25 551-B1. 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 copolymeric polycarboxylates is generally 2,000 to 150,000, preferably 5,000 to 100,000.
  • Suitable aminopolycarboxylic acid is nitrilotriacetic acid in the form of its sodium salt. Its proportion can be up to 10% by weight, preferably up to 5% by weight. Also useful are ethylenediaminetetraacetic acid and its higher homologs such as diethylenetriaminepentaacetic acid, which are also present as sodium salts. Examples of preferred polyphosphonic acids or their salts are 1-hydroxyethane-1,1-diphosphonate, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate, each in the form of the sodium salt. The proportion of these additives can be up to 2% by weight, generally up to 1% by weight, based on the granules.
  • Particularly suitable anionic surfactants have been found to be sulfonates and fatty acid soaps, each of which is preferably in the form of sodium salts.
  • Suitable are alkylbenzenesulfonates with linear C9 ⁇ 13 alkyl chains, especially dodecylbenzenesulfonate, linear alkanesulfonates with 11 to 15 carbon atoms, as can be obtained by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, alphasulfofatty acid salts and their esters, which are derived from saturated C12 ⁇ 18 fatty acids and lower alcohols such as methanol, ethanol and propanol, and olefin sulfonates such as z.
  • Preferred surfactants are the alkyl benzene sulfonates defined above.
  • Suitable soaps are those of saturated and / or unsaturated C12 ⁇ 22 fatty acids, for example from coconut, palm kernel or tallow fatty acids and soaps obtained from hydrogenated rapeseed oil fatty acids.
  • the anionic surfactants are generally in the form of sodium salts.
  • the total anionic surfactant content of the tablets is 3 to 20, preferably 5 to 15,% by weight. Of these, 3 to 15% by weight, in particular 5 to 10% by weight, are preferably sulfonate surfactants and 0 to 10, preferably 0.5 to 5 and in particular 1 to 3% by weight of soap.
  • Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thioalcohols, fatty acid amides and fatty acids. 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.
  • Preferred nonionic surfactants from the class of polyglycol ethers are derived from alcohols with 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.
  • 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
  • ethylation products with corresponding chain and EO distribution available from other native fatty alcohol mixtures.
  • ethoxylated oxo alcohols for example, those of the composition C12 ⁇ 15 with 5 to 10 EO and C14-C15 with 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 made of tallow alcohol with 3 to 6 EO and tallow alcohol with 12 to 16 EO or C13 ⁇ 15 oxo alcohol with 5 EO and C12 ⁇ 14 -Oxo alcohol with 8 to 12 EO.
  • ethoxylates containing EO groups and PO groups e.g. B. C12 ⁇ 18 alcohols of the formula R- (PO) a - (EO) b or R- (EO) b - (PO) c , in which a numbers from 1 to 3, b such from 5 to 20 and c Numbers from 1 to 10 (b greater than c) mean.
  • the total content of nonionic surfactants in the tablets can be 3 to 15, preferably 4 to 10% by weight.
  • Optional components of the tablet-like agents are neutral salts such as sodium sulfate, anti-graying agents, in particular cellulose ethers, optical brighteners, dyes and fragrances, biocides, tabletting aids, bleaching persalts such as sodium perborate (as mono- or tetrahydrate), bleach activators such as tetraacetyl ethylene diamine diamine diamine inhibitor and foam inhibitor, as well as organo-diaminodiaminoxinoxysiloxysiloxane, and foam inhibitors such as organopolysethane, as well as foam inhibitors , Paraffins, microcrystalline paraffins and bis-acyl-alkylenediamines derived from C16 ⁇ 20 fatty acids.
  • neutral salts such as sodium sulfate, anti-graying agents, in particular cellulose ethers, optical brighteners, dyes and fragrances, biocides, tabletting aids, bleaching persalts such as sodium perborate (as mono- or t
  • the tablets are manufactured in several stages.
  • the first stage at least two granular powder components (A) and (B) are first produced separately, which are dry mixed in a second stage.
  • further powdery to granular additives can also be added.
  • These include those already mentioned Tableting aids, tablet disintegrants, persalts, bleach activators, enzymes and foam inhibitors.
  • Liquid additives the proportion of which is generally small, can also be mixed in at this time, such as fragrances and liquid or melted foam inhibitors. Because of their low content, they are easily adsorbed without impairing the pourability and tablettability of the dry mixtures.
  • the powder component (A) contains the total amount of the anionic surfactants used.
  • This component can consist exclusively of anionic surfactants or can also contain a part of the zeolite or the other skeletal salts (builder salts) as well as common detergent components such as neutral salts, optical brighteners and anti-graying substances.
  • component (A) consists exclusively of anionic surfactants, for example alkylbenzenesulfonate or soap, these are preferably in the form of granular granules, flakes or extrudates.
  • component (A) preferably contains part of the total zeolite present, the builder salts and, if appropriate, the other detergent constituents.
  • the powder component (A) contains zeolite, it can also have low levels of nonionic surfactants. These small amounts of non-ionic surfactants in (A), which are therefore largely harmless to the solution behavior of the tablet, can be incorporated into the powder component together with the zeolite if the latter is present in the form of a water-containing, stable dispersion (masterbatch). Such zeolite dispersions are often stabilized by adding nonionic surfactants, especially low ethoxylated fatty alcohols. The proportion of such nonionic surfactants is usually 1 to 5% by weight, based on anhydrous zeolite (0.5 to 2% by weight, based on aqueous zeolite dispersion). However, if component (A) contains no zeolite, it is preferably free of nonionic surfactants.
  • the powder component (A) can also be divided into 2 or more individual components, for example into a sub-component which contains the sulfonate surfactant and part of the other solids and a second sub-component which consists of soap particles.
  • the soap particles can also be agglomerated with some of the solids.
  • the powder component (B) contains the main amount, preferably the total amount of the total nonionic surfactants used, and carriers on which these nonionic surfactants are adsorbed.
  • Suitable carriers are zeolite, the aforementioned water-soluble skeletal salts, sodium sulfate and other solids commonly used in detergents, such as cellulose ethers, in particular carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and hydroxyalkyl-cellulose mixed ethers.
  • Mixtures of the abovementioned carriers are preferably used, in particular mixtures of zeolite and sodium sulfate, mixtures of zeolite and salts of (co) polymeric carboxylic acids and, if appropriate, additionally sodium sulfate, mixtures of zeolite and cellulose ethers (also if appropriate with the addition of sodium sulfate), but especially mixtures of all mentioned carriers.
  • the content of powder component (B) on carriers on the one hand and on nonionic surfactants on the other hand should be selected so that the grains are still free-flowing and non-sticky.
  • the grains can be powdered on the surface to prevent sticking.
  • Zeolites, neutral salts and cellulose ethers as well as known adsorbents, e.g. B. finely divided silica.
  • the proportion of water-insoluble powdering agents should not or not significantly exceed 3% by weight, based on the powder component, in order to counteract a reduction in the disintegration and dissolving properties.
  • the two powder components can be prepared in a manner known per se, for example by spray drying aqueous batches (slurries) or by mixing the respective individual components under granulating conditions or by compacting, for. B. plasticizing, extruding and then crushing the plasticized mixtures to a suitable grain size. Both powder components can be produced in the same or different ways.
  • the procedure is preferably such that, in the preparation of powder component (B), an aqueous batch (slurry) is first spray-dried which contains zeolite and salts of (co) polymeric carboxylic acids and, if appropriate, sodium sulfate.
  • Optical brighteners and cellulose ethers suitable as graying inhibitors can also be used in this way. Due to their porous structure, the granular products formed during spray drying have a very high adsorption capacity for liquid or fat-like substances, in particular nonionic surfactants and also perfume oils. They are therefore sprayed or mixed with the liquid or melted nonionic surfactants after the spray drying, and they can absorb up to 40% by weight thereof. With this adsorption process, a desired increase in bulk density from 300 to 450 g / l to 500 to 700 g / l (grams per liter) is achieved at the same time.
  • the preferred production method for the powder component (A) is granulation, which can be carried out continuously or in batches in conventional granulating devices.
  • the solids such as soda, sodium sulfate, sodium silicate and zeolite can be presented in dry form and the anionic surfactants in neutralized form (salt form) mixed in as aqueous solutions under granulating conditions.
  • the excess water is removed at the same time or in a subsequent drying process.
  • the neutralized solutions of the anionic surfactants in particular those of alkylbenzenesulfonates and soaps, are pasty or highly viscous in concentrated form and must therefore be diluted with water in order to be processed. However, this requires increased drying effort.
  • the free sulfonic acids in particular pure or high-strength aqueous alkylbenzenesulfonate pastes, which (if appropriate in a mixture with free fatty acids) are neutralized in the mixer with equivalent amounts or a slight excess of high-strength sodium hydroxide solution (e.g. 50% strength) will.
  • the other solids such as sodium carbonate, sodium silicate, sodium sulfate and zeolite are mixed in, with granulation occurring at the same time as a result of mechanical processing.
  • the zeolite can also be used as an aqueous dispersion (masterbatch).
  • the moist granules are then dried, the proportion of moisture (corresponding to a loss of water at a drying temperature of 140 ° C.) being below 10% by weight, preferably below 5% by weight.
  • the stated method of production favors the formation of high bulk weights and thus small packaging volumes without impairing the disintegration and dissolving properties.
  • the powder component (A) can also be coated or powdered before further processing, the ones already mentioned Fabrics can be used. This coating prevents intimate contact with the nonionic surfactants in component (B) and can therefore improve the disintegration and dissolution properties of the tablet or prevent powder components from sticking to the tablet press.
  • the two powder components advantageously have a bulk density of 400 to 1000 g / l, preferably 500 to 900 g / l.
  • Their average grain size is 0.2 to 1.2 mm, the proportion of particles less than 0.05 mm being less than 1% by weight and that of particles more than 2 mm less than 5% by weight.
  • other powder components can also be used. These include per compounds such as sodium perborate, which is present as a tetrahydrate or monohydrate. If bleach activators such as tetraacetylethylenediamine are also used, they are preferably used in granular form, cellulose ethers and starch ethers having proven useful as granulation aids, especially since they also act as release agents against the per compound. Likewise, enzymes and foam inhibitors are preferably used in granulated or coated form in order to avoid an activity-reducing interaction with the other tablet components.
  • per compounds such as sodium perborate, which is present as a tetrahydrate or monohydrate.
  • bleach activators such as tetraacetylethylenediamine are also used, they are preferably used in granular form, cellulose ethers and starch ethers having proven useful as granulation aids, especially since they also act as release agents against the per compound.
  • enzymes and foam inhibitors are preferably used in granulated or coated form in order to
  • tablet auxiliaries can be admixed which improve the tablettability or prevent powder residues from sticking to the pressing tools, increase the breaking strength and / or promote the disintegration of the tablet in cold water and the dispersion and dissolution of the tablet ingredients.
  • Suitable auxiliaries include depolymerized starch, starch ether, sodium sulfate, sodium chloride and in particular sodium acetate and trisodium citrate. The latter two salts are preferably used in the form containing water of crystallization.
  • the proportion of tablet auxiliaries can be up to 15% by weight, preferably 0.5 to 5% by weight. They are preferably used as fine-grain powders with an average grain size of less than 0.5 mm, in particular less than 0.2 mm.
  • Tableting can be carried out in conventional tablet presses.
  • the press rams and dies can be coated in a suitable manner, for example with Teflon. Common procedures, such as lifting the die from the tablet surface with a rotary motion, can also be used.
  • the compression ratio should be between 1: 1.2 and 1: 2.5, preferably 1: 1.3 and 1: 1.6 in order to achieve sufficient strength.
  • the pressures are between 200 and 1200 kg / cm2, preferably 300 and 1000 kg / cm2.
  • the dimensions of the tablet can be arbitrary.
  • ratios of tablet height to tablet diameter have been from 1: 1 to 1: 2, preferably from 1: 1.2 to 1: 1.8 with a diameter of 4 to 8 cm, preferably from 5 to 7 cm, particularly proven.
  • compositions data in% by weight, based on the total amount in the tablet).
  • Other tablet components are listed under C, which can be added as further components.
  • the total amount of ingredients (a) to (c) is preferably 10 to 20% by weight, that of zeolite (d) is preferably 20 to 35% by weight, that of sodium sulfate (g) is preferably 0 to 20% by weight. %, the cellulose ether (h) preferably 0.5 to 2% by weight, the polycarboxylate preferably 1.5 to 5% by weight and the water 1 to 5% by weight.
  • individual powder components can also be colored.
  • the powder component (A) was prepared in such a way that a heated paste of dodecylbenzenesulfonic acid (linear C10 ⁇ 13 alkyl radicals) was neutralized with 50% NaOH in a mixer. Under granulating conditions, further solids and an aqueous dispersion of zeolite stabilized with 5-fold ethoxylated tallow alcohol were then used.
  • dodecylbenzenesulfonic acid linear C10 ⁇ 13 alkyl radicals
  • the granules had a bulk density of 720 g / l and an average grain size of 0.5 mm.
  • the polymeric carboxylate consisted of the sodium salt of a copolymer of 70% by weight acrylic acid and 30% by weight maleic acid.
  • the powder component (B) was prepared by spray drying an aqueous slurry containing zeolite (from an aqueous dispersion, stabilized with 5-fold ethoxylated tallow alcohol) and polymeric carboxylate.
  • a 1 4 mixture of 3-fold ethoxylated coconut alcohol and 5-fold ethoxylated tallow alcohol with an optical brightener suspended in it and perfume oil was sprayed onto the porous, spray-dried grains.
  • the grains then had the following composition: Parts by weight Zeolite (22% bound water) 9.0 Tallow alcohol + 5 EO 0.2 Polymeric carboxylate 1.2 nonionic mixture of surfactants 4.2 optical brightener 0.1 Perfume 0.2 humidity 0.4
  • the powder component had a bulk density of 680 g / l and an average grain size of 0.4 mm.
  • Powder component A Parts by weight Powder component A 50.6 Powder component B 15.3 Defoamer granules 0.8 Enzyme granules 1.5 Sodium perborate tetrahydrate 24.7 TAED granules 2.1 Sodium acetate trihydrate 5.0
  • the defoamer granules consisted of a polysiloxane, granulated with sodium sulfate as the carrier material and carboxymethyl cellulose as the granulating aid (silicone content 10%).
  • the TAED granules consisted of 94% tetraacetylethylene diamine, granulated with 5% carboxymethyl cellulose (balance water). These granules and the enzyme granules were stained with a green dye.
  • the powder mixture was pressed into tablets in a tablet press (type Exakt 31), tablets with a diameter of 51 mm and a height of 35 mm being obtained from in each case 85 g of mixture.
  • the tablets obtained had a breaking strength of 5 kg (lowest load in kg at which the tablets broke).
  • the tablet dimensions did not change within 2 months as well as no decrease in breaking strength. Only the weight of the tablets increased slightly, ie by 2 to 3%.
  • component (A) contained in the powder component (B) were mixed in during the granulation process and the granules obtained were processed into tablets in the same way, between 15 and 30% by weight of the tablet remained undissolved in the flushing device after the flushing-in period had ended.

Abstract

A washing powder in tablet-form, containing phosphate-free or low-phosphate builder salts, anionic tensides and non-ionic tensides, is produced by first preparing two powdery to granular components (A) and (B) separately and by then mixing and compressing them. Component (A) contains the total mass of the anionic tensides while component (B) contains 75 to 100 weight percent of the total mass of the non-ionic tensides.

Description

Waschmitteltabletten besitzen gegenüber pulverförmigen Mitteln eine Reihe von Vorteilen, wie einfache Dosierung und geringer Bedarf an Verpackungsvolumen. Probleme ergeben sich jedoch da­durch, daß zur Erreichung einer hinreichenden Form- und Bruch­beständigkeit beim Verpressen der pulverförmigen Rohstoffe ver­hältnismäßig hohe Preßdrucke angewendet werden müssen. Auf­grund der starken Verdichtung weisen derartige Tabletten viel­fach unzureichende Zerfalls- und Lösungseigenschaften bei der Anwendung auf mit der Folge, daß ungelöste Teile in den Ein­spülkammern der Waschmaschinen zurückbleiben. Diese Probleme existierten bereits bei phosphatreichen, d. h. 50 Gew.-% und mehr an Tripolyphosphat (TPP) enthaltenden Tabletten und wur­den teilweise dadurch gelöst, daß man bestimmte TPP-Modifika­tionen verwendete bzw. eine Teilhydrolyse des TPP vornahm; vergleiche hierzu US 3,081,267, US 3,461,074, DE 11 91 509, DE 12 71 884 und DE 14 67 595 (GB 1 041 036).Detergent tablets have a number of advantages over powdered detergents, such as simple dosing and low packaging volume requirements. Problems arise, however, in that relatively high compression pressures have to be used to achieve adequate dimensional stability and fracture resistance when pressing the powdered raw materials. Because of the high degree of compaction, such tablets often have inadequate disintegration and dissolving properties when used, with the result that undissolved parts remain in the washing-up compartments of the washing machines. These problems already exist with phosphate-rich, i.e. H. Tablets containing 50% by weight and more of tripolyphosphate (TPP) and were partially dissolved by using certain TPP modifications or by partial hydrolysis of the TPP; compare US 3,081,267, US 3,461,074, DE 11 91 509, DE 12 71 884 and DE 14 67 595 (GB 1 041 036).

Für die Herstellung phosphatreduzierter, insbesondere phosphat­freier Tabletten sind derartige Lösungsvorschläge ungeeignet. Hier ergeben vielmehr zusätzliche Probleme dadurch, daß die als besonders umweltfreundlich geltenden phosphatsubstituierenden Zeolithe wasserunlöslich sind und den Zerfall der Tablette in Wasser behindern. Eine zusätzliche Schwierigkeit ergibt sich bei der Mitverwendung nichtionischer Tenside, auf die in neuzeit­lichen, bei 40 bis 60 oC anzuwendenden Waschmitteln nicht ver­ zichtet werden kann. Es hat sich gezeigt, daß der Zerfalls- und Lösungsprozeß erheblich verzögert wird, wenn die zur Verpres­sung bestimmten pulverförmigen bzw. granularen Gemische neben Zeolith noch anionaktive Tenside neben nichtionischen Tensiden enthalten. Auch bei Anwendung zusätzlicher Tablettensprengmittel lassen sich aus derartigen Gemischen mit den üblichen Hilfsmitteln keine Waschmitteltabletten herstellen, die gleichzeitig gut löslich und hinreichend bruchfest sind.Such proposed solutions are unsuitable for the production of phosphate-reduced, in particular phosphate-free tablets. Rather, additional problems arise here in that the phosphate-substituting zeolites, which are considered to be particularly environmentally friendly, are water-insoluble and hinder the disintegration of the tablet in water. An additional difficulty arises when using nonionic surfactants, which are not used in modern detergents used at 40 to 60 ° C can be waived. It has been shown that the disintegration and dissolution process is considerably delayed if the powdery or granular mixtures intended for compression contain, in addition to zeolite, anionic surfactants in addition to nonionic surfactants. Even when additional tablet disintegrants are used, it is not possible to produce detergent tablets from such mixtures with the usual auxiliaries, which are at the same time readily soluble and sufficiently break-resistant.

Durch die vorliegende Erfindung wird dieses Problem gelöst.This problem is solved by the present invention.

Gegenstand der Erfindung ist ein Verfahren zur Herstellung phosphatreduzierter, feinteilige Zeolithe, Gerüstsalze, anionische Tenside und nichtionische Tenside aus der Klasse der Polyglykol­etherderivate enthaltende Waschmittel in Tablettenform, dadurch gekennzeichnet, daß man mindestens zwei zuvor hergestellte pul­verförmige bis granulare Komponenten (A) und (B) vermischt und dieses Gemisch verpreßt, wobei die Komponenten

  • (A) die Gesamtmenge der anionischen Tenside,
  • (B) 75 bis 100 Gew.-% der Gesamtmenge der nichtionischen Ten­side enthalten.
The invention relates to a process for the preparation of reduced-phosphate, finely divided zeolites, skeletal salts, anionic surfactants and nonionic surfactants from the class of detergents in tablet form containing polyglycol ether derivatives, characterized in that at least two previously prepared powdery to granular components (A) and (B) mixed and this mixture pressed, the components
  • (A) the total amount of anionic surfactants,
  • (B) 75 to 100% by weight of the total amount of the nonionic surfactants.

Vorzugsweise soll das Gewichtsverhältnis von anionischem Tensid zu nichtionischem Tensid in Komponente (A) ein Verhältnis von 10 : 1 nicht unterschreiten.The weight ratio of anionic surfactant to nonionic surfactant in component (A) should preferably not be less than a ratio of 10: 1.

Unter "phosphatreduziert" im Sinne der Erfindung sind solche Mittel zu verstehen, die weniger als 10 Gew.-%, vorzugsweise weniger als 5 Gew.-% und insbesondere weniger als 1 Gew.-% Phosphat enthalten, berechnet als wasserfreies Pentanatrium­triphosphat. In einer besonders bevorzugten Ausführungsform sind die Mittel phosphatfrei.“Phosphate-reduced” in the context of the invention is to be understood as meaning those compositions which contain less than 10% by weight, preferably less than 5% by weight and in particular less than 1% by weight of phosphate, calculated as anhydrous pentasodium triphosphate. In a particularly preferred embodiment, the agents are phosphate-free.

Die Mittel enthalten feinkristallinen Zeolith als Phosphatsubstitut in Mengen von 10 bis 40 Gew.-%, vorzugsweise 20 bis 35 Gew.-%. Geeignete Zeolithe sind solche 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) beträgt 1 bis 10 µm. Ihr Calciumbindevermögen, das nach den Angaben der DE 24 12 837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g.The compositions contain fine crystalline zeolite as a phosphate substitute in amounts of 10 to 40% by weight, preferably 20 to 35% by weight. Suitable zeolites are those 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 1 to 10 µm. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g.

Die Mittel enthalten weiterhin wasserlösliche Gerüstsalze mit wasserenthärtenden bzw. sequestrierenden Eigenschaften. Hierzu zählen Waschalkalien wie Natriumcarbonat, Natriumsilikate der Zusammensetzung Na₂O : SiO₂ = 1 : 1 bis 1 : 3,3 sowie Salze polyanionischer Verbindungen aus der Klasse der homopolymeren bzw. copolymeren Carbonsäuren, der Aminopolycarbonsäuren und der Polyphosphonsäuren. Meist werden Waschalkalien und seque­strierende polyanionische Verbindungen gemeinsam verwendet.The agents also contain water-soluble skeletal salts with water-softening or sequestering properties. These include washing alkalis such as sodium carbonate, sodium silicates with the composition Na₂O: SiO₂ = 1: 1 to 1: 3.3 and salts of polyanionic compounds from the class of homopolymeric or copolymeric carboxylic acids, aminopolycarboxylic acids and polyphosphonic acids. Mostly washing alkalis and sequestering polyanionic compounds are used together.

Beispiele für homopolymere und/oder copolymere Carbonsäuren bzw. deren wasserlöslichen Salze, von denen die Natriumsalze bevorzugt verwendet werden, sind Polyacrylsäure, Polymethacryl­säure und Polymaleinsäure, Copolymere der Acrylsäure mit Meth­acrylsäure bzw. Copolymere der 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 50 Molprozent, vorzugsweise weniger als 30 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 Gew.-% Acrylsäure und 55 bis 15 Gew.-% Maleinsäure anwesend sind. Das Molekulargewicht der homo- bzw. copolymeren Polycarboxylate beträgt im allgemeinen 2000 bis 150000, vorzugs­weise 5000 bis 100000.Examples of homopolymeric and / or copolymeric carboxylic acids or their water-soluble salts, of which the sodium salts are preferably used, are polyacrylic acid, polymethacrylic acid and polymaleic acid, copolymers of acrylic acid with methacrylic acid or copolymers of 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 50 mole percent, preferably less than 30 mole percent. Copolymers of acrylic acid have proven particularly suitable or methacrylic acid with maleic acid, as described in more detail, for example, in EP 25 551-B1. 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 copolymeric polycarboxylates is generally 2,000 to 150,000, preferably 5,000 to 100,000.

Als Aminopolycarbonsäure kommt Nitrilotriessigsäure in Form ihres Natriumsalzes in Betracht. Sein Anteil kann bis 10 Gew.-%, be­vorzugt bis 5 Gew.-% betragen. Brauchbar sind ferner Ethylendi­amintetraessigsäure und deren höhere Homologen wie Diethylentri­aminpentaessigsäure, die ebenfalls als Natriumsalze vorliegen. Beispiele für bevorzugte Polyphosphonsäuren bzw. deren Salze sind 1-Hydroxyethan-1,1-diphosphonat, Ethylendiamin-tetramethy­lenphosphonat und Diethylentriamin-pentamethylenphosphonat, jeweils in Form des Natriumsalzes. Der Anteil dieser Zusätze kann bis 2 Gew.-%, im allgemeinen bis 1 Gew.-%, bezogen auf das Granulat betragen.Suitable aminopolycarboxylic acid is nitrilotriacetic acid in the form of its sodium salt. Its proportion can be up to 10% by weight, preferably up to 5% by weight. Also useful are ethylenediaminetetraacetic acid and its higher homologs such as diethylenetriaminepentaacetic acid, which are also present as sodium salts. Examples of preferred polyphosphonic acids or their salts are 1-hydroxyethane-1,1-diphosphonate, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate, each in the form of the sodium salt. The proportion of these additives can be up to 2% by weight, generally up to 1% by weight, based on the granules.

Als geeignete anionische Tenside haben sich insbesondere Sul­fonate und fettsaure Seifen erwiesen, die jeweils bevorzugt als Natriumsalze vorliegen. Geeignet sind Alkylbenzolsulfonate mit linearen C₉₋₁₃-Alkylketten, insbesondere Dodecylbenzolsulfonat, lineare Alkansulfonate mit 11 bis 15 C-Atomen, wie sie durch Sulfochlorierung bzw. Sulfoxidation von Alkanen und anschlie­ßende Verseifung bzw. Neutralisation erhältlich sind, alphasul­fofettsaure Salze sowie deren Ester, die sich von gesättigten C₁₂₋₁₈-Fettsäuren und niederen Alkoholen wie Methanol, Ethanol und Propanol ableiten, und Olefinsulfonate, wie sie z. B. durch SO₃-Sulfonierung entständiger C₁₂₋₁₈-Olefine und anschließende alkalische Hydrolyse gebildet werden. Bevorzugte Tenside sind die oben definierten Alkylbenzolsulfonate. Als Seifen kommen solche von gesättigten und/oder ungesättigten C₁₂₋₂₂-Fettsäuren in Frage, beispielsweise aus Kokos-, Palmkern- oder Talgfettsäuren sowie aus hydrierten Rübölfettsäuren gewonnene Seifen. Die anionischen Tenside liegen im allgemeinen als Natriumsalze vor.Particularly suitable anionic surfactants have been found to be sulfonates and fatty acid soaps, each of which is preferably in the form of sodium salts. Suitable are alkylbenzenesulfonates with linear C₉₋₁₃ alkyl chains, especially dodecylbenzenesulfonate, linear alkanesulfonates with 11 to 15 carbon atoms, as can be obtained by sulfochlorination or sulfoxidation of alkanes and subsequent saponification or neutralization, alphasulfofatty acid salts and their esters, which are derived from saturated C₁₂₋₁₈ fatty acids and lower alcohols such as methanol, ethanol and propanol, and olefin sulfonates such as z. B. by SO₃-sulfonation final C₁₂₋₁₈ olefins and subsequent alkaline hydrolysis. Preferred surfactants are the alkyl benzene sulfonates defined above. Suitable soaps are those of saturated and / or unsaturated C₁₂₋₂₂ fatty acids, for example from coconut, palm kernel or tallow fatty acids and soaps obtained from hydrogenated rapeseed oil fatty acids. The anionic surfactants are generally in the form of sodium salts.

Der Gehalt der Tabletten an anionischen Tensiden beträgt ins­gesamt 3 bis 20, vorzugsweise 5 bis 15 Gew.-%. Davon entfallen vorzugsweise 3 bis 15 Gew.-%, insbesondere 5 bis 10 Gew.-% auf Sulfonattenside und 0 bis 10, vorzugsweise 0,5 bis 5 und insbe­sondere 1 bis 3 Gew.-% auf Seife.The total anionic surfactant content of the tablets is 3 to 20, preferably 5 to 15,% by weight. Of these, 3 to 15% by weight, in particular 5 to 10% by weight, are preferably sulfonate surfactants and 0 to 10, preferably 0.5 to 5 and in particular 1 to 3% by weight of soap.

Geeignete nichtionische Tenside sind Alkoxylierungsprodukte mit 10 bis 20 Kohlenstoffatomen im hydrophoben Rest und 3 bis 20 Glykolethergruppen. Hierzu zählen Ethoxylierungsprodukte von Alkoholen, vicinalen Diolen, Aminen, Thioalkoholen, Fettsäure­amiden und Fettsäuren. 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.Suitable nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, amines, thioalcohols, fatty acid amides and fatty acids. 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.

Bevorzugte nichtionische Tenside aus der Klasse der Polyglykol­ether leiten sich von Alkoholen mit 12 bis 18 C-Atomen ab. 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 was­serlösliche bzw. in Wasser dispergierbare Gemische von Verbin­dungen mit unterschiedlichem Alkoxylierungsgrad. Die Zahl der EO- bzw. PO-Gruppen entspricht dem statistischen Mittelwert.Preferred nonionic surfactants from the class of polyglycol ethers are derived from alcohols with 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.

Beispiele für geeignete ethoxylierte Fettalkohole sind C₁₂₋₁₈-­Cocosalkohole mit 3 bis 12 EO, C₁₆₋₁₈-Talgalkohol mit 4 bis 16Examples of suitable ethoxylated fatty alcohols are C₁₂₋₁₈ coconut alcohols with 3 to 12 EO, C₁₆₋₁₈ tallow alcohol with 4 to 16

EO, Oleylalkohol mit 4 bis 12 EO sowie aus anderen nativen Fett­alkoholgemischen erhältliche Ethylierungsprodukte entsprechender Ketten- und EO-Verteilung. Aus der Reihe der ethoxylierten Oxoalkohole sind beispielsweise solche der Zusammensetzung C₁₂₋₁₅ mit 5 bis 10 EO und C₁₄-C₁₅ mit 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 mit 3 bis 6 EO und Talgalkohol mit 12 bis 16 EO oder C₁₃₋₁₅-Oxoalkohol mit 5 EO und C₁₂₋₁₄-Oxoalkohol mit 8 bis 12 EO. Weiterhin sind auch Ethoxylate geeignet, die EO-Gruppen und PO-Gruppen enthalten, z. B. C₁₂₋₁₈-Alkohole der Formel R-(PO)a-(EO)b bzw. R-(EO)b-(PO)c, worin a Zahlen von 1 bis 3, b solche von 5 bis 20 und c Zahlen von 1 bis 10 (b größer als c) bedeuten.EO, oleyl alcohol with 4 to 12 EO as well as ethylation products with 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 with 5 to 10 EO and C₁₄-C₁₅ with 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 made of tallow alcohol with 3 to 6 EO and tallow alcohol with 12 to 16 EO or C₁₃₋₁₅ oxo alcohol with 5 EO and C₁₂₋₁₄ -Oxo alcohol with 8 to 12 EO. Also suitable are ethoxylates containing EO groups and PO groups, e.g. B. C₁₂₋₁₈ alcohols of the formula R- (PO) a - (EO) b or R- (EO) b - (PO) c , in which a numbers from 1 to 3, b such from 5 to 20 and c Numbers from 1 to 10 (b greater than c) mean.

Der Gesamtgehalt der Tabletten an nichtionischen Tensiden kann 3 bis 15, vorzugsweise 4 bis 10 Gew.-% betragen.The total content of nonionic surfactants in the tablets can be 3 to 15, preferably 4 to 10% by weight.

Fakultative Bestandteile der tablettenförmigen Mittel sind Neu­tralsalze wie Natriumsulfat, vergrauungsverhütende Mittel, ins­besondere Celluloseether, optische Aufheller, Farb- und Duft­stoffe, Biocide, Tablettierhilfsmittel, bleichend wirkende Persalze wie Natriumperborat (als Mono- oder Tetrahydrat), Bleichaktiva­toren wie Tetraacetylethylendiamin, Enzyme sowie Schauminhibi­toren wie Organopolysiloxane, Paraffine, mikrokristalline Paraffine und von C₁₆₋₂₀-Fettsäuren abgeleitete Bis-acyl-alkylendiamine.Optional components of the tablet-like agents are neutral salts such as sodium sulfate, anti-graying agents, in particular cellulose ethers, optical brighteners, dyes and fragrances, biocides, tabletting aids, bleaching persalts such as sodium perborate (as mono- or tetrahydrate), bleach activators such as tetraacetyl ethylene diamine diamine diamine inhibitor and foam inhibitor, as well as organo-diaminodiaminoxinoxysiloxysiloxane, and foam inhibitors such as organopolysethane, as well as foam inhibitors , Paraffins, microcrystalline paraffins and bis-acyl-alkylenediamines derived from C₁₆₋₂₀ fatty acids.

Die Herstellung der Tabletten erfolgt in mehreren Stufen. In der 1. Stufe werden zunächst mindestens zwei granulare Pulverkompo­nenten (A) und (B) getrennt voneinander hergestellt, die in einer 2. Stufe trocken miteinander vermischt werden. In dieser Mischstufe können auch weitere pulverförmige bis granulare Zu­satzstoffe zugemischt werden. Hierzu zählen die bereits erwähnten Tablettierhilfsmittel, Tablettensprengmittel, Persalze, Bleich­aktivatoren, Enzyme und Schauminhibitoren. Flüssige Zusatzstof­fe, deren Anteil im allgemeinen gering ist, können ebenfalls zu diesem Zeitpunkt zugemischt werden, wie Duftstoffe und flüssige bzw. geschmolzene Schauminhibitoren. Wegen ihres geringen An­teils werden sie problemlos adsorbiert, ohne die Schüttfähigkeit und Tablettierbarkeit der trockenen Gemische zu beeinträchtigen.The tablets are manufactured in several stages. In the first stage, at least two granular powder components (A) and (B) are first produced separately, which are dry mixed in a second stage. In this mixing stage, further powdery to granular additives can also be added. These include those already mentioned Tableting aids, tablet disintegrants, persalts, bleach activators, enzymes and foam inhibitors. Liquid additives, the proportion of which is generally small, can also be mixed in at this time, such as fragrances and liquid or melted foam inhibitors. Because of their low content, they are easily adsorbed without impairing the pourability and tablettability of the dry mixtures.

Die Pulverkomponente (A) enthält die Gesamtmenge der eingesetz­ten anionischen Tenside. Diese Komponente kann ausschließlich aus anionischen Tensiden bestehen oder auch einen Teil des Zeoliths bzw. der sonstigen Gerüstsalze (Buildersalze) sowie üblicher Waschmittelbestandteile wie Neutralsalze, optische Aufheller und vergrauungsverhütenden Stoffe enthalten. Sofern die Komponente (A) ausschließlich aus anionischen Tensiden be­steht, beispielsweise aus Alkylbenzolsulfonat oder Seife, liegen diese vorzugsweise als körnige Granulate, Schuppen oder Extru­date vor. Bevorzugt enthält die Komponente (A) jedoch einen Teil des insgesamt anwesenden Zeoliths, der Buildersalze und gege­benenfalls der sonstigen Waschmittelbestandteile. Sofern die Pulverkomponente (A) Zeolith enthält, kann sie auch geringe Ge­halte an nichtionischen Tensiden aufweisen. Diese geringen und daher für das Lösungsverhalten der Tablette weitgehend unschäd­lichen Anteile an nichtionischen Tensiden in (A) können zusammen mit dem Zeolith in die Pulverkomponente eingebracht werden, wenn dieser von der Herstellung her als wasserhaltige, stabile Dispersion (masterbatch) vorliegt. Derartige Zeolith-Dispersionen werden vielfach durch Zusätze nichtionischer Tenside, insbesondere niedrig ethoxylierter Fettalkohole, stabilisiert. Der Anteil an derartigen nichtionischen Tensiden liegt meist bei 1 bis 5 Gew.-%, bezogen auf wasserfreien Zeolith (0,5 bis 2 Gew.-% bezogen auf wäßrige Zeolith-Dispersion). Sofern jedoch die Komponente (A) keinen Zeolith enthält, ist sie vorzugsweise frei von nichtionischen Tensiden.The powder component (A) contains the total amount of the anionic surfactants used. This component can consist exclusively of anionic surfactants or can also contain a part of the zeolite or the other skeletal salts (builder salts) as well as common detergent components such as neutral salts, optical brighteners and anti-graying substances. If component (A) consists exclusively of anionic surfactants, for example alkylbenzenesulfonate or soap, these are preferably in the form of granular granules, flakes or extrudates. However, component (A) preferably contains part of the total zeolite present, the builder salts and, if appropriate, the other detergent constituents. If the powder component (A) contains zeolite, it can also have low levels of nonionic surfactants. These small amounts of non-ionic surfactants in (A), which are therefore largely harmless to the solution behavior of the tablet, can be incorporated into the powder component together with the zeolite if the latter is present in the form of a water-containing, stable dispersion (masterbatch). Such zeolite dispersions are often stabilized by adding nonionic surfactants, especially low ethoxylated fatty alcohols. The proportion of such nonionic surfactants is usually 1 to 5% by weight, based on anhydrous zeolite (0.5 to 2% by weight, based on aqueous zeolite dispersion). However, if component (A) contains no zeolite, it is preferably free of nonionic surfactants.

Gegebenenfalls kann die Pulverkomponente (A) auch in 2 oder mehr Einzelkomponenten unterteilt sein, beispielsweise in eine Teilkomponente, welche das Sulfonat-Tensid und einen Teil der übrigen Feststoffe enthält und eine zweite Teilkomponente, die aus Seifenpartikeln besteht. Auch die Seifenpartikel können in einer weiteren Ausführungsform mit einem Teil der Feststoffe agglomeriert sein.If appropriate, the powder component (A) can also be divided into 2 or more individual components, for example into a sub-component which contains the sulfonate surfactant and part of the other solids and a second sub-component which consists of soap particles. In a further embodiment, the soap particles can also be agglomerated with some of the solids.

Die Pulverkomponente (B) enthält die Hauptmenge, vorzugsweise die Gesamtmenge der insgesamt eingesetzten nichtionischen Ten­side sowie Trägerstoffe, an denen diese nichtionischen Tenside adsorbiert sind. Als Trägerstoffe eignen sich Zeolith, die vor­erwähnten wasserlöslichen Gerüstsalze, Natriumsulfat und weitere in Waschmitteln üblicherweise verwendeten Feststoffe wie Cellu­loseether, insbesondere Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulose und Hydryalkyl-alkylcellulose-Mischether. Bevorzugt werden Gemische der genannten Trägerstoffe verwen­det, insbesondere Gemische aus Zeolith und Natriumsulfat, Ge­mische aus Zeolith und Salzen (co-)polymerer Carbonsäuren und gegebenenfalls zusätzlich Natriumsulfat, Gemische aus Zeolith und Celluloseethern (auch dies gegebenenfalls unter Zusatz von Na­triumsulfat), insbesondere jedoch Gemische aller genannten Trä­gerstoffe. Weiterhin hat es sich als zweckmäßig erwiesen, auch die fakultativ anwesenden optischen Aufheller, Duftstoffe und Biocide in die Pulverkomponente (B) zu inkorporieren. Sofern bei der Herstellung der Pulverkomponente (B) auf die Anwendung hö­herer Temperaturen, beispielsweise Sprühtrocknungstemperaturen verzichtet wird, können auch Perverbindungen wie Natriumperbo­rat (als Mono- oder Tetrahydrat) als Trägerstoffkomponente mit­verwendet werden.The powder component (B) contains the main amount, preferably the total amount of the total nonionic surfactants used, and carriers on which these nonionic surfactants are adsorbed. Suitable carriers are zeolite, the aforementioned water-soluble skeletal salts, sodium sulfate and other solids commonly used in detergents, such as cellulose ethers, in particular carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and hydroxyalkyl-cellulose mixed ethers. Mixtures of the abovementioned carriers are preferably used, in particular mixtures of zeolite and sodium sulfate, mixtures of zeolite and salts of (co) polymeric carboxylic acids and, if appropriate, additionally sodium sulfate, mixtures of zeolite and cellulose ethers (also if appropriate with the addition of sodium sulfate), but especially mixtures of all mentioned carriers. Furthermore, it has proven to be expedient to also incorporate the optional optical brighteners, fragrances and biocides into the powder component (B). If the use of higher temperatures, for example spray drying temperatures, is dispensed with in the preparation of the powder component (B), per compounds such as sodium perborate (as mono- or tetrahydrate) can also be used as the carrier component.

Der Gehalt der Pulverkomponente (B) an Trägerstoffen einerseits und an nichtionischen Tensiden andererseits soll so gewählt werden, daß die Körner noch rieselfähig und nicht klebend sind.The content of powder component (B) on carriers on the one hand and on nonionic surfactants on the other hand should be selected so that the grains are still free-flowing and non-sticky.

Gegebenenfalls können die Körner oberflächlich gepudert sein, um ein Kleben zu unterbinden. Als Puderungsmittel eignen sich insbesondere Zeolithe, Neutralsalze und Celluloseether sowie be­kannte Adsorptionsmittel, z. B. feinteilige Kieselsäure. Der Anteil wasserunlöslicher Puderungsmittel sollte 3 Gew -%, bezogen auf die Pulverkomponente, nicht oder nicht wesentlich übersteigen, um einer Verminderung der Zerfalls- und Lösungseigenschaften entgegenzuwirken.If necessary, the grains can be powdered on the surface to prevent sticking. Zeolites, neutral salts and cellulose ethers as well as known adsorbents, e.g. B. finely divided silica. The proportion of water-insoluble powdering agents should not or not significantly exceed 3% by weight, based on the powder component, in order to counteract a reduction in the disintegration and dissolving properties.

Die Herstellung der beiden Pulverkomponenten kann in an sich bekannter Weise erfolgen, beispielsweise durch Sprühtrocknen wäßriger Ansätze (Slurries) oder durch Vermischen der jeweiligen Einzelkomponenten unter granulierenden Bedingungen oder durch Kompaktieren, z. B. Plastifizieren, Extrudieren und anschlie­ßendes Zerkleinern der plastifizierten Gemische auf eine geeignete Korngröße. Beide Pulverkomponenten können in gleicher oder verschiedener Weise hergestellt werden.The two powder components can be prepared in a manner known per se, for example by spray drying aqueous batches (slurries) or by mixing the respective individual components under granulating conditions or by compacting, for. B. plasticizing, extruding and then crushing the plasticized mixtures to a suitable grain size. Both powder components can be produced in the same or different ways.

Vorzugsweise wird so verfahren, daß man bei der Herstellung der Pulverkomponente (B) zunächst einen wäßrigen Ansatz (Slurry) sprühtrocknet, der Zeolith und Salze (co-)polymerer Carbonsäu­ren sowie gegebenenfalls Natriumsulfat enthält. Auch optische Aufheller und als Vergrauungsinhibitoren geeignete Celluloseether können auf diese Weise mitverwendet werden. Die bei der Sprüh­trocknung entstehenden körnigen Produkte weisen aufgrund ihrer porösen Struktur ein sehr hohes Adsorptionsvermögen für flüssige bzw. fettartige Stoffe, insbesondere nichtionische Tenside und auch Parfümöle auf. Sie werden daher im Anschluß an die Sprüh­trocknung mit den flüssigen bzw. geschmolzenen nichtionischen Tensiden besprüht bzw. vermischt, wobei sie bis zu 40 Gew.-% davon aufnehmen können. Mit diesem Adsorptionsvorgang wird gleichzeitig eine erwünschte Erhöhung des Schüttgewichtes von 300 bis 450 g/l auf 500 bis 700 g/l (Gramm pro Liter) erzielt.The procedure is preferably such that, in the preparation of powder component (B), an aqueous batch (slurry) is first spray-dried which contains zeolite and salts of (co) polymeric carboxylic acids and, if appropriate, sodium sulfate. Optical brighteners and cellulose ethers suitable as graying inhibitors can also be used in this way. Due to their porous structure, the granular products formed during spray drying have a very high adsorption capacity for liquid or fat-like substances, in particular nonionic surfactants and also perfume oils. They are therefore sprayed or mixed with the liquid or melted nonionic surfactants after the spray drying, and they can absorb up to 40% by weight thereof. With this adsorption process, a desired increase in bulk density from 300 to 450 g / l to 500 to 700 g / l (grams per liter) is achieved at the same time.

Bevorzugte Herstellungsweise für die Pulverkomponente (A) ist die Granulation, die in üblichen Granuliervorrichtungen konti­nuierlich oder chargenweise durchgeführt werden kann. Man kann beispielsweise die Feststoffe wie Soda, Natriumsulfat, Natrium­silikat und Zeolith in trockener Form vorlegen und die anionischen Tenside in neutralisierter Form (Salzform) als wäßrige Lösungen unter granulierenden Bedingungen hinzumischen. Das überschüs­sige Wasser wird gleichzeitig oder in einem nachgeschalteten Trocknungsprozeß entfernt. Die neutralisierten Lösungen der Aniontenside, insbesondere die von Alkylbenzolsulfonaten und Seifen sind in konzentrierter Form jedoch pastös bzw. hochviskos und müssen daher, um verarbeitet werden zu können, mit Wasser verdünnt werden. Dies erfordert jedoch einen erhöhten Trock­nungsaufwand.The preferred production method for the powder component (A) is granulation, which can be carried out continuously or in batches in conventional granulating devices. For example, the solids such as soda, sodium sulfate, sodium silicate and zeolite can be presented in dry form and the anionic surfactants in neutralized form (salt form) mixed in as aqueous solutions under granulating conditions. The excess water is removed at the same time or in a subsequent drying process. However, the neutralized solutions of the anionic surfactants, in particular those of alkylbenzenesulfonates and soaps, are pasty or highly viscous in concentrated form and must therefore be diluted with water in order to be processed. However, this requires increased drying effort.

Vorzugsweise geht man daher von den freien Sulfonsäuren aus, insbesondere reinen oder hochprozentigen wäßrigen Alkylbenzolsulfonat-Pasten, die (gegebenenfalls im Gemisch mit freien Fettsäuren) im Mischer mit äquivalenten Mengen oder einem geringen Überschuß an hochprozentiger Natronlauge (z. B. 50%ig) neutralisiert werden. Hierzu werden die übrigen Feststoffe wie Natriumcarbonat, Natriumsilikat, Natriumsulfat und Zeolith zugemischt, wobei gleichzeitig durch mechanische Bearbeitung eine Granulation eintritt. Der Zeolith kann auch als wäßrige Dispersion (masterbatch) eingesetzt werden. Die feuchten Granulate werden anschließend getrocknet, wobei der Anteil der Feuchtigkeit (ent­sprechend einem Wasserverlust bei einer Trocknungstemperatur von 140 oC) unter 10 Gew.-%, vorzugsweise unter 5 Gew.-% liegen soll. Die angegebene Herstellungsweise begünstigt die Ausbildung hoher Schüttgewichte und damit kleiner Verpackungsvolumina ohne Beeinträchtigung der Zerfalls- und Lösungseigenschaften.It is therefore preferred to start from the free sulfonic acids, in particular pure or high-strength aqueous alkylbenzenesulfonate pastes, which (if appropriate in a mixture with free fatty acids) are neutralized in the mixer with equivalent amounts or a slight excess of high-strength sodium hydroxide solution (e.g. 50% strength) will. For this purpose, the other solids such as sodium carbonate, sodium silicate, sodium sulfate and zeolite are mixed in, with granulation occurring at the same time as a result of mechanical processing. The zeolite can also be used as an aqueous dispersion (masterbatch). The moist granules are then dried, the proportion of moisture (corresponding to a loss of water at a drying temperature of 140 ° C.) being below 10% by weight, preferably below 5% by weight. The stated method of production favors the formation of high bulk weights and thus small packaging volumes without impairing the disintegration and dissolving properties.

Auch die Pulverkomponente (A) kann vor ihrer Weiterverarbeitung beschichtet bzw. gepudert werden, wobei die bereits genannten Stoffe eingesetzt werden können. Diese Beschichtung verhindert einen innigen Kontakt mit den nichtionischen Tensiden in der Komponente (B) und kann somit die Zerfalls- und Lösungseigen­schaften der Tablette verbessern bzw. das Kleben von Pulver­bestandteilen an der Tablettenpresse verhindern.The powder component (A) can also be coated or powdered before further processing, the ones already mentioned Fabrics can be used. This coating prevents intimate contact with the nonionic surfactants in component (B) and can therefore improve the disintegration and dissolution properties of the tablet or prevent powder components from sticking to the tablet press.

Die beiden Pulverkomponenten weisen zweckmäßigerweise ein Schüttgewicht von 400 bis 1000 g/l vorzugsweise von 500 bis 900 g/l auf. Ihre mittlere Korngröße beträgt 0,2 bis 1,2 mm, wobei der Anteil an Partikeln unter 0,05 mm weniger als 1 Gew.-% und der an Partikeln mit mehr als 2 mm unter 5 Gew.-% betragen soll.The two powder components advantageously have a bulk density of 400 to 1000 g / l, preferably 500 to 900 g / l. Their average grain size is 0.2 to 1.2 mm, the proportion of particles less than 0.05 mm being less than 1% by weight and that of particles more than 2 mm less than 5% by weight.

Außer den beiden obligatorischen Komponenten (A) und (B) kön­nen noch weitere Pulverkomponenten eingesetzt werden. Hierzu zählen Perverbindungen wie Natriumperborat, das als Tetrahydrat oder Monohydrat vorliegt. Sofern Bleichaktivatoren wie Tetra­acetylethylendiamin mitverwendet werden, kommen sie vorzugs­weise in granulierter Form zum Einsatz, wobei sich Celluloseether und Stärkeether als Granulationshilfsmittel bewährt haben, zumal sie gleichzeitig als Trennmittel gegenüber der Perverbindung wirken. Ebenso kommen Enzyme und Schauminhibitoren bevorzugt in granulierter bzw. umhüllter Form zum Einsatz, um eine akti­vitätsmindernde Wechselwirkung mit den übrigen Tablettenbe­standteilen zu vermeiden.In addition to the two mandatory components (A) and (B), other powder components can also be used. These include per compounds such as sodium perborate, which is present as a tetrahydrate or monohydrate. If bleach activators such as tetraacetylethylenediamine are also used, they are preferably used in granular form, cellulose ethers and starch ethers having proven useful as granulation aids, especially since they also act as release agents against the per compound. Likewise, enzymes and foam inhibitors are preferably used in granulated or coated form in order to avoid an activity-reducing interaction with the other tablet components.

Weiterhin können Tablettenhilfsmittel zugemischt werden, welche die Tablettierbarkeit verbessern bzw. das Ankleben von Pulver­resten an den Preßwerkzeugen verhindern, die Bruchfestigkeit erhöhen und/oder den Zerfall der Tablette in kaltem Wasser und das Dispergieren und Lösung der Tabletteninhabsstoffe fördern. Zu den geeigneten Hilfsstoffen zählen depolymierisierte Stärke, Stärkeether, Natriumsulfat, Natriumchlorid und insbesondere Na­triumacetat und Trinatriumcitrat. Die beiden letztgenannten Salze kommen bevorzugt in der Kristallwasser enthaltenden Form zum Einsatz. Der Anteil der Tablettenhilfsmittel kann bis zu 15 Gew.-%, vorzugsweise 0,5 bis 5 Gew.-% betragen. Sie kommen be­vorzugt als feinkörnige Pulver mit einer mittleren Korngröße unter 0,5 mm, insbesondere unter 0,2 mm zum Einsatz.In addition, tablet auxiliaries can be admixed which improve the tablettability or prevent powder residues from sticking to the pressing tools, increase the breaking strength and / or promote the disintegration of the tablet in cold water and the dispersion and dissolution of the tablet ingredients. Suitable auxiliaries include depolymerized starch, starch ether, sodium sulfate, sodium chloride and in particular sodium acetate and trisodium citrate. The latter two salts are preferably used in the form containing water of crystallization. The proportion of tablet auxiliaries can be up to 15% by weight, preferably 0.5 to 5% by weight. They are preferably used as fine-grain powders with an average grain size of less than 0.5 mm, in particular less than 0.2 mm.

Das Tablettieren kann in üblichen Tablettenpressen durchgeführt werden. Zwecks Verhinderung eines Anbackens von Pulverbestand­teilen können die Preßstempel und Matrizen in geeigneter Weise beschichtet sein, beispielsweise mit Teflon. Ebenso können übliche Verfahrensweisen, wie Abheben des Prägestempels von der Tablet­tenoberfläche unter Drehbewegung, angewendet werden. Das Ver­dichtungsverhältnis soll zwecks Erzielung einer ausreichenden Festigkeit zwischen 1 : 1,2 und 1 : 2,5, vorzugsweise 1 : 1,3 und 1 : 1,6 liegen. Die Preßdrucke liegen zwischen 200 und 1200 kg/cm², vorzugsweise 300 und 1000 kg/cm². Die Abmessungen der Tablette können an sich beliebig sein. Für eine Anwendung in Haushaltswaschmaschinen, die mit übichen Einspülkammern ausge­rüstet sind, haben sich jedoch Verhältnisse von Tablettenhöhe zu Tablettendurchmesser von 1 : 1 bis 1 : 2, vorzugsweise von 1 : 1,2 bis 1 : 1,8 bei einem Druchmesser von 4 bis 8 cm, vor­zugsweise von 5 bis 7 cm, besonders bewährt.Tableting can be carried out in conventional tablet presses. In order to prevent powder constituents from baking on, the press rams and dies can be coated in a suitable manner, for example with Teflon. Common procedures, such as lifting the die from the tablet surface with a rotary motion, can also be used. The compression ratio should be between 1: 1.2 and 1: 2.5, preferably 1: 1.3 and 1: 1.6 in order to achieve sufficient strength. The pressures are between 200 and 1200 kg / cm², preferably 300 and 1000 kg / cm². The dimensions of the tablet can be arbitrary. For use in household washing machines which are equipped with conventional induction chambers, ratios of tablet height to tablet diameter have been from 1: 1 to 1: 2, preferably from 1: 1.2 to 1: 1.8 with a diameter of 4 to 8 cm, preferably from 5 to 7 cm, particularly proven.

Es folgen Beispiele für geeignete Zusammensetzungen (Angaben in Gew.-%, bezogen auf die Gesamtmenge in der Tablette). Unter C sind sonstige Tablettenbestandteile aufgeführt, die als weitere Komponenten zugemischt werden können. Beispiele Komponenten A B C a) Na-Dodecylbenzolsulfonat 5 - 15 vorzugsweise 6 - 12 b) Seife, C12-18, Na-Salz 0 - 5 vorzugsweise 0,5 - 3 c) C12-18-Alkohol + 3-15 EO 0 - 1 3 - 15 vorzugsweise 0,2 - 0,8 4 - 10 d) Zeolith NaA (22% H₂O) 0 - 30 4 - 20 vorzugsweise 10 - 25 5 - 15 e) Na-Silikat 0 - 10 vorzugsweise 1 - 5 f) Na-Carbonat 0 - 30 0 - 10 vorzugsweise 2 - 10 g) Na-Sulfat 0 - 20 0 - 20 0 - 10 vorzugsweise 0 - 10 h) Celluloseether 0 - 2 0 - 1 0 - 2 vorzugsweise 0,5 - 1 i) Polycarboxylat 0 - 5 0 - 5 vorzugsweise 1 - 4 0,5 - 3 j) Tablettierungshilfsmittel 0 - 15 vorzugsweise 2 - 10 k) Na-Perborat 0 - 25 vorzugsweise 5 - 10 l) Bleichaktivator (TAED) 0 - 5 vorzugsweise 0,5 - 3 m) Enzyme, Entschäumer, Duftstoffe 0 - 3 n) optische Aufheller 0 - 0,5 0 - 0,5 o) Wasser 0,5 - 5 0,5 - 5 The following are examples of suitable compositions (data in% by weight, based on the total amount in the tablet). Other tablet components are listed under C, which can be added as further components. Examples Components A B C. a) Na dodecylbenzenesulfonate 5 - 15 preferably 6-12 b) Soap, C 12-18 , Na salt 0 - 5 preferably 0.5 - 3 c) C 12-18 alcohol + 3-15 EO 0 - 1 3 - 15 preferably 0.2-0.8 4 - 10 d) zeolite NaA (22% H₂O) 0-30 4 - 20 preferably 10 - 25 5 - 15 e) Na silicate 0-10 preferably 1 - 5 f) Na carbonate 0-30 0-10 preferably 2 - 10 g) Na sulfate 0 - 20 0 - 20 0-10 preferably 0-10 h) cellulose ether 0-2 0 - 1 0-2 preferably 0.5 - 1 i) polycarboxylate 0 - 5 0 - 5 preferably 1 - 4 0.5 - 3 j) Tableting aids 0 - 15 preferably 2 - 10 k) Na perborate 0 - 25 preferably 5 - 10 l) bleach activator (TAED) 0 - 5 preferably 0.5 - 3 m) enzymes, defoamers, fragrances 0-3 n) optical brighteners 0 - 0.5 0 - 0.5 o) water 0.5 - 5 0.5 - 5

Die Gesamtmenge der Inhaltsstoffe (a) bis (c) beträgt dabei vor­zugsweise 10 bis 20 Gew.-%, die des Zeoliths (d) vorzugsweise 20 bis 35 Gew.-%, die des Natriumsulfats (g) vorzugsweise 0 bis 20 Gew.-%, des Celluloseethers (h) vorzugsweise 0,5 bis 2 Gew.-%, des Polycarboxylats vorzugsweise 1,5 bis 5 Gew.-% und des Was­sers 1 bis 5 Gew.-%. Schließlich können einzelne Pulverkompo­nenten auch noch angefärbt sein.The total amount of ingredients (a) to (c) is preferably 10 to 20% by weight, that of zeolite (d) is preferably 20 to 35% by weight, that of sodium sulfate (g) is preferably 0 to 20% by weight. %, the cellulose ether (h) preferably 0.5 to 2% by weight, the polycarboxylate preferably 1.5 to 5% by weight and the water 1 to 5% by weight. Finally, individual powder components can also be colored.

Beispielexample

Die Herstellung der Pulverkomponente (A) erfolgte in der Weise, daß in einem Mischer eine erwärmte Paste aus Dodecylbenzolsul­fonsäure (lineare C₁₀₋₁₃-Alkylreste) mit 50%iger NaOH neutra­lisiert wurde. Unter granulierenden Bedingungen wurden dann weitere Feststoffe sowie eine wäßrige Dispersion von Zeolith, stabilisiert mit 5fach ethoxyliertem Talgalkohol, eingesetzt. Nach dem Trocknen mit erwärmter Luft wurden Granulate folgender Zu­sammensetzung erhalten: Gewichtsteile Alkylbenzolsulfonat 7,3 Na-Talgseife 1,5 Zeolith NaA 21,2 Talgalkohol + 5 EO 0,5 Na-Carbonat 6,6 Na-Sulfat 5,0 Na-Silikat (1 : 3,3) 3,0 Polymeres Carboxylat 3,0 Na-Carboxymethylcellulose 0,7 Feuchtigkeit 1,8 The powder component (A) was prepared in such a way that a heated paste of dodecylbenzenesulfonic acid (linear C₁₀₋₁₃ alkyl radicals) was neutralized with 50% NaOH in a mixer. Under granulating conditions, further solids and an aqueous dispersion of zeolite stabilized with 5-fold ethoxylated tallow alcohol were then used. After drying with heated air, granules of the following composition were obtained: Parts by weight Alkyl benzene sulfonate 7.3 Na tallow soap 1.5 Zeolite NaA 21.2 Tallow alcohol + 5 EO 0.5 Na carbonate 6.6 Na sulfate 5.0 Na silicate (1: 3.3) 3.0 Polymeric carboxylate 3.0 Na carboxymethyl cellulose 0.7 humidity 1.8

Das Granulat wies ein Schüttgewicht von 720 g/l und eine mittlere Korngröße von 0,5 mm auf. Das polymere Carboxylat bestand aus dem Natriumsalz eines Copolymeren aus 70 Gew.-% Acrylsäure und 30 Gew.-% Maleinsäure.The granules had a bulk density of 720 g / l and an average grain size of 0.5 mm. The polymeric carboxylate consisted of the sodium salt of a copolymer of 70% by weight acrylic acid and 30% by weight maleic acid.

Die Pulverkomponente (B) wurde durch Sprühtrocknen eines wäß­rigen Slurries hergestellt, enthaltend Zeolith (aus einer wäßrigen Dispersion, stabilisiert mit 5fach ethoxyliertem Talgalkohol) und polymeres Carboxylat. Auf die porösen, sprühgetrockneten Körner wurde eine 1 : 4-Mischung aus 3fach ethoxyliertem Cocosalkohol und 5fach ethoxyliertem Talgalkohol mit darin suspendiertem op­tischen Aufheller sowie Parfümöl aufgesprüht. Die Körner wiesen danach die folgende Zusammensetzung auf: Gewichtsteile Zeolith (22 % gebundenes Wasser) 9,0 Talgalkohol + 5 EO 0,2 Polymeres Carboxylat 1,2 nichtionisches Tensidgemisch 4,2 optischer Aufheller 0,1 Parfüm 0,2 Feuchtigkeit 0,4 The powder component (B) was prepared by spray drying an aqueous slurry containing zeolite (from an aqueous dispersion, stabilized with 5-fold ethoxylated tallow alcohol) and polymeric carboxylate. A 1: 4 mixture of 3-fold ethoxylated coconut alcohol and 5-fold ethoxylated tallow alcohol with an optical brightener suspended in it and perfume oil was sprayed onto the porous, spray-dried grains. The grains then had the following composition: Parts by weight Zeolite (22% bound water) 9.0 Tallow alcohol + 5 EO 0.2 Polymeric carboxylate 1.2 nonionic mixture of surfactants 4.2 optical brightener 0.1 Perfume 0.2 humidity 0.4

Die Pulverkomponente wies ein Schüttgewicht von 680 g/l und eine mittlere Korngröße von 0,4 mm auf.The powder component had a bulk density of 680 g / l and an average grain size of 0.4 mm.

Folgende Pulverkomponenten wurden miteinander vermischt: Gewichtsteile Pulverkomponente A 50,6 Pulverkomponente B 15,3 Entschäumergranulat 0,8 Enzymgranulat 1,5 Natriumperborat-tetrahydrat 24,7 TAED-Granulat 2,1 Natriumacetat-trihydrat 5,0 The following powder components were mixed together: Parts by weight Powder component A 50.6 Powder component B 15.3 Defoamer granules 0.8 Enzyme granules 1.5 Sodium perborate tetrahydrate 24.7 TAED granules 2.1 Sodium acetate trihydrate 5.0

Das Entschäumergranulat bestand aus einem Polysiloxan, granu­liert mit Natriumsulfat als Trägermaterial und Carboxymethyl­cellulose als Granulierhilfsmittel (Silikon-Gehalt 10 %). Das TAED-Granulat bestand aus 94 % Tetraacetylethylendiamin, granu­liert mit 5 % Carboxymethylcellulose (Rest Wasser). Diese Gra­nulate sowie das Enzymgranulat waren mit einem grünen Farbstoff angefärbt.The defoamer granules consisted of a polysiloxane, granulated with sodium sulfate as the carrier material and carboxymethyl cellulose as the granulating aid (silicone content 10%). The TAED granules consisted of 94% tetraacetylethylene diamine, granulated with 5% carboxymethyl cellulose (balance water). These granules and the enzyme granules were stained with a green dye.

Das Pulvergemisch wurde in einer Tablettenpresse (Typ Exakt 31) zu Tabletten verpreßt, wobei aus jeweils 85 g Gemisch Tabletten mit einem Durchmesser von 51 mm und einer Höhe von 35 mm er­halten wurden. Die erhaltenen Tabletten wiesen eine Bruchfe­stigkeit von 5 kg auf (niedrigste Belastung in kg, bei der ein Bruck der Tabletten auftritt) Bei offener Lagerung (20 bis 25 oC, 50 % bis 80 % relative Luftfeuchtigkeit) trat innerhalb 2 Monaten keine Änderung der Tablettenabmessungen sowie kein Rückgang der Bruchfestigkeit auf. Lediglich das Gewicht der Tabletten nahm geringfügig, d. h. um 2 bis 3 % zu.The powder mixture was pressed into tablets in a tablet press (type Exakt 31), tablets with a diameter of 51 mm and a height of 35 mm being obtained from in each case 85 g of mixture. The tablets obtained had a breaking strength of 5 kg (lowest load in kg at which the tablets broke). When stored open (20 to 25 ° C., 50% to 80% relative humidity), the tablet dimensions did not change within 2 months as well as no decrease in breaking strength. Only the weight of the tablets increased slightly, ie by 2 to 3%.

Die Tabletten lösten sich in üblichen Haushaltswaschmaschinen während der programmierten Einspülperiode rückstandsfrei auf.The tablets dissolved in normal household washing machines during the programmed wash-in period without leaving any residue.

Wurden die in der Pulverkomponente (B) enthaltenden Bestand­teile der Komponente (A) während des Granulierprozesses zuge­mischt und die erhaltenen Granulate in gleicher Weise zu Ta­bletten verarbeitet, verblieben nach Beendigung der Einspül­periode zwischen 15 und 30 Gew.-% der Tablette ungelöst in der Einspülvorrichtung.If the constituents of component (A) contained in the powder component (B) were mixed in during the granulation process and the granules obtained were processed into tablets in the same way, between 15 and 30% by weight of the tablet remained undissolved in the flushing device after the flushing-in period had ended.

Claims (8)

1. Verfahren zur Herstellung phosphatreduzierter, feinteilige Zeolithe, Gerüstsalze, anionische Tenside und nichtionische Tenside aus der Klasse der Polyglykoletherderivate enthal­tende Waschmittel in Tablettenform, dadurch gekennzeichnet, daß man mindestens zwei zuvor hergestellte pulverförmige bis granulare Komponenten (A) und (B) vermischt und dieses Gemisch verpreßt, wobei die Komponenten (A) die Gesamtmenge der anionischen Tenside, (B) 75 bis 100 Gew.-% der Gesamtmenge der nichtionischen Ten­side enthalten. 1. A process for the preparation of reduced-phosphate, finely divided zeolites, skeletal salts, anionic surfactants and nonionic surfactants from the class of detergents in tablet form containing polyglycol ether derivatives, characterized in that at least two previously prepared powdery to granular components (A) and (B) are mixed and this Mixture pressed, the components (A) the total amount of anionic surfactants, (B) 75 to 100% by weight of the total amount of the nonionic surfactants. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Gewichtsverhältnis von anionischem Tensid zu nicht­ionischem Tensid in Komponente (A) ein Verhältnis von 10 : 1 nicht unterschreitet.2. The method according to claim 1, characterized in that the weight ratio of anionic surfactant to nonionic surfactant in component (A) does not fall below a ratio of 10: 1. 3. Verfahren nach Anspruch 1 und 2, dadurch gekennzeichnet, daß man von phosphatfreien Gemischen ausgeht.3. The method according to claim 1 and 2, characterized in that one starts from phosphate-free mixtures. 4. Verfahren nach Ansprüchen 1 bis 3, dadurch gekennzeich­net, daß man die anionischen Tenside in einer Menge von 3 bis 20 Gew.-%, vorzugsweise 5 bis 15 Gew.-%, bezogen auf das Gesamtgewicht der Tablette einsetzt.4. Process according to Claims 1 to 3, characterized in that the anionic surfactants are used in an amount of 3 to 20% by weight, preferably 5 to 15% by weight, based on the total weight of the tablet. 5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man bis 10 Gew.-%, vorzugsweise 0,5 bis 5 Gew.-% an Seife einsetzt.5. The method according to claim 3, characterized in that one uses up to 10 wt .-%, preferably 0.5 to 5 wt .-% of soap. 6. Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die nichtionischen Tenside in einer Menge von 3 bis 15 Gew.-%, vorzugsweise 4 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Tablette ein­setzt.6. The method according to one or more of claims 1 to 5, characterized in that the nonionic surfactants in an amount of 3 to 15 wt .-%, preferably 4 to 10 % By weight, based on the total weight of the tablet. 7. Verfahren nach einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man weitere Pulverkomponenten zumischt, welche die Eigenschaften der Tablette bzw. der Wasch- und Bleichaktivität der damit hergestellten Wasch­lauge verbessern.7. The method according to one or more of claims 1 to 6, characterized in that further powder components are added which improve the properties of the tablet or the washing and bleaching activity of the wash liquor thus produced. 8. Waschmitteltablette mit einem Gehalt an feinteiligen Zeolithen phosphatarmen bis phosphatfreien Gerüstsalzen, anionischen Tensiden und nichtionischen Tensiden aus der Klasse der Polyglykolether, dadurch gekennzeichnet, daß die Tablette aus einem innigen Gemisch von mindestens zwei pulverförmi­gen bis granularen Pulverkomponenten (A) und (B) zusam­mengesetzt ist, wobei die Komponenten (A) die Gesamtmenge der anionischen Tenside, (B) 75 bis 100 Gew.-% der Gesamtmenge der nichtionischen Ten­side enthalten. 8. Detergent tablet containing fine-particle zeolites low-phosphate to phosphate-free skeletal salts, anionic surfactants and nonionic surfactants from the class of polyglycol ethers, characterized in that the tablet is composed of an intimate mixture of at least two powdery to granular powder components (A) and (B) is, the components (A) the total amount of anionic surfactants, (B) 75 to 100% by weight of the total amount of the nonionic surfactants.
EP89114911A 1988-08-17 1989-08-11 Method for the production of low phosphate detergent tablets Pending EP0355626A1 (en)

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Publication number Priority date Publication date Assignee Title
WO1991015567A2 (en) * 1990-04-02 1991-10-17 Henkel Kommanditgesellschaft Auf Aktien Process for the manufacture of washing and cleansing agents
EP0466485A2 (en) * 1990-07-13 1992-01-15 Unilever Plc Detergent compositions
JPH04285699A (en) * 1990-10-19 1992-10-09 Unilever Nv Detergent composition
WO1992018604A1 (en) * 1991-04-12 1992-10-29 Henkel Kommanditgesellschaft Auf Aktien Process for producing detergent tablets for dishwashing machines
WO1993000419A1 (en) * 1991-06-27 1993-01-07 Henkel Kommanditgesellschaft Auf Aktien Method for the production of cleaing-agent tablets for machine dishwashing
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WO1999018185A1 (en) * 1997-10-04 1999-04-15 Henkel Kommanditgesellschaft Auf Aktien Method for producing stabile and rapidly dissolving washing detergent tablets
WO1999024545A2 (en) * 1997-11-11 1999-05-20 Henkel Kommanditgesellschaft Auf Aktien Method for producing stable, rapidly decomposing shaped bodies of detergent
WO2000000582A1 (en) * 1998-06-26 2000-01-06 Henkel Kommanditgesellschaft Auf Aktien Method for producing detergent shaped bodies
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EP0994179A2 (en) * 1998-10-14 2000-04-19 Henkel Kommanditgesellschaft auf Aktien Zeolite compound containing shaped detergent bodies
WO2000043487A1 (en) * 1999-01-22 2000-07-27 Henkel Kommanditgesellschaft Auf Aktien Abrasion-resistant moulded detergent and/or cleaning agent articles
WO2000044871A1 (en) * 1999-01-28 2000-08-03 Henkel Kommanditgesellschaft Auf Aktien Abrasion-resistant moulded detergent and cleaning agent articles with a high non-ionic surface-active agent content
WO2000050559A1 (en) * 1999-02-25 2000-08-31 Henkel Kommanditgesellschaft Auf Aktien Abrasion-resistant washing and cleaning agent shaped bodies containing solid additives
WO2000053716A1 (en) * 1999-03-11 2000-09-14 Henkel Kommanditgesellschaft Auf Aktien Moulded washing and cleaning agents with a surfactant/builder combination
WO2000060048A1 (en) * 1999-04-03 2000-10-12 Henkel Kommanditgesellschaft Auf Aktien Detergent forms with special tenside granulates
WO2000078910A1 (en) * 1999-06-19 2000-12-28 Henkel Kommanditgesellschaft Auf Aktien Moulding method for detergent and cleansing agent tablets
WO2001019952A1 (en) * 1999-09-15 2001-03-22 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
WO2001034756A1 (en) * 1999-11-09 2001-05-17 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
WO2001034759A1 (en) * 1999-11-11 2001-05-17 The Procter & Gamble Company Bleach-containing detergent tablets
WO2001034761A1 (en) * 1999-11-09 2001-05-17 Cognis Deutschland Gmbh & Co. Kg Surfactant granules with improved dissolution rate
US6472362B1 (en) 1997-10-22 2002-10-29 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions in tablet form
EP1133548B2 (en) † 1998-11-27 2006-07-12 Unilever Plc Detergent compositions in tablet form

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DE4404279A1 (en) * 1994-02-10 1995-08-17 Henkel Kgaa Tablet with builder substances
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DE69731189T3 (en) † 1997-05-27 2009-12-24 The Procter & Gamble Company, Cincinnati Tablets and process for their preparation
CN1131300C (en) 1997-05-30 2003-12-17 尤尼利弗公司 Free-flowing particulate detergent compsns.
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ATE228561T1 (en) 1998-10-09 2002-12-15 Unilever Nv WATER SOFTENING AND DETERGENT COMPOSITIONS
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DE19851442A1 (en) * 1998-11-09 2000-05-11 Henkel Kgaa Detergent tablets with finely divided solubilizers
GB9911949D0 (en) 1999-05-21 1999-07-21 Unilever Plc Detergent compositions
GB9913549D0 (en) 1999-06-10 1999-08-11 Unilever Plc Detergent compositions
GB9913551D0 (en) 1999-06-10 1999-08-11 Unilever Plc Cleaning compositions
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WO1991015567A3 (en) * 1990-04-02 1991-11-14 Henkel Kgaa Process for the manufacture of washing and cleansing agents
WO1991015567A2 (en) * 1990-04-02 1991-10-17 Henkel Kommanditgesellschaft Auf Aktien Process for the manufacture of washing and cleansing agents
US5382377A (en) * 1990-04-02 1995-01-17 Henkel Kommanditgesellschaft Auf Aktien Process for the production of detergents
AU636776B2 (en) * 1990-07-13 1993-05-06 Unilever Plc Detergent compositions in the form of tablets
EP0466485A2 (en) * 1990-07-13 1992-01-15 Unilever Plc Detergent compositions
EP0466485A3 (en) * 1990-07-13 1992-03-04 Unilever Plc Detergent compositions
US5225100A (en) * 1990-07-13 1993-07-06 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions
JPH04285699A (en) * 1990-10-19 1992-10-09 Unilever Nv Detergent composition
US5358655A (en) * 1991-04-12 1994-10-25 Henkel Kommanditgesellschaft Auf Aktien Process for the production of detergent tablets for dishwashing machines
WO1992018604A1 (en) * 1991-04-12 1992-10-29 Henkel Kommanditgesellschaft Auf Aktien Process for producing detergent tablets for dishwashing machines
WO1993000419A1 (en) * 1991-06-27 1993-01-07 Henkel Kommanditgesellschaft Auf Aktien Method for the production of cleaing-agent tablets for machine dishwashing
EP0598586A1 (en) * 1992-11-16 1994-05-25 Unilever Plc Detergent compositions
WO1999018185A1 (en) * 1997-10-04 1999-04-15 Henkel Kommanditgesellschaft Auf Aktien Method for producing stabile and rapidly dissolving washing detergent tablets
US6472362B1 (en) 1997-10-22 2002-10-29 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions in tablet form
WO1999024545A2 (en) * 1997-11-11 1999-05-20 Henkel Kommanditgesellschaft Auf Aktien Method for producing stable, rapidly decomposing shaped bodies of detergent
WO1999024545A3 (en) * 1997-11-11 1999-07-15 Henkel Kgaa Method for producing stable, rapidly decomposing shaped bodies of detergent
WO2000000581A1 (en) * 1998-06-26 2000-01-06 Henkel Kommanditgesellschaft Auf Aktien Method for producing detergent shaped bodies
WO2000000582A1 (en) * 1998-06-26 2000-01-06 Henkel Kommanditgesellschaft Auf Aktien Method for producing detergent shaped bodies
EP0994179A3 (en) * 1998-10-14 2000-06-07 Henkel Kommanditgesellschaft auf Aktien Zeolite compound containing shaped detergent bodies
EP0994179A2 (en) * 1998-10-14 2000-04-19 Henkel Kommanditgesellschaft auf Aktien Zeolite compound containing shaped detergent bodies
EP1133548B2 (en) † 1998-11-27 2006-07-12 Unilever Plc Detergent compositions in tablet form
WO2000043487A1 (en) * 1999-01-22 2000-07-27 Henkel Kommanditgesellschaft Auf Aktien Abrasion-resistant moulded detergent and/or cleaning agent articles
WO2000044871A1 (en) * 1999-01-28 2000-08-03 Henkel Kommanditgesellschaft Auf Aktien Abrasion-resistant moulded detergent and cleaning agent articles with a high non-ionic surface-active agent content
WO2000050559A1 (en) * 1999-02-25 2000-08-31 Henkel Kommanditgesellschaft Auf Aktien Abrasion-resistant washing and cleaning agent shaped bodies containing solid additives
WO2000053716A1 (en) * 1999-03-11 2000-09-14 Henkel Kommanditgesellschaft Auf Aktien Moulded washing and cleaning agents with a surfactant/builder combination
WO2000060048A1 (en) * 1999-04-03 2000-10-12 Henkel Kommanditgesellschaft Auf Aktien Detergent forms with special tenside granulates
WO2000078910A1 (en) * 1999-06-19 2000-12-28 Henkel Kommanditgesellschaft Auf Aktien Moulding method for detergent and cleansing agent tablets
WO2001019952A1 (en) * 1999-09-15 2001-03-22 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
WO2001034756A1 (en) * 1999-11-09 2001-05-17 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
WO2001034761A1 (en) * 1999-11-09 2001-05-17 Cognis Deutschland Gmbh & Co. Kg Surfactant granules with improved dissolution rate
US7199096B1 (en) 1999-11-09 2007-04-03 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
WO2001034759A1 (en) * 1999-11-11 2001-05-17 The Procter & Gamble Company Bleach-containing detergent tablets

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DK26991A (en) 1991-02-15
WO1990002165A1 (en) 1990-03-08

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