DE19923626A1 - Production of surfactant granulates, useful for making laundry tablets, involves converting sugar surfactant to compound with water-soluble carrier material and granulating with non-aqueous solvent - Google Patents

Abstract

Production of surfactant granulates containing nonionic surfactant comprises: (a) converting sugar surfactant to a compound in the presence of water-soluble carrier material; and then (b) mixing the compound with a non-aqueous solvent and granulating the mixture in known manner, optionally with addition of other constituents of laundry detergents.

Description

The present invention relates to a process for producing surfactant granules, containing nonionic surfactants, wherein the granules via a two-stage process getting produced.

Provide compacted or highly concentrated detergent powder or tablets constitute a significant proportion of the detergents and cleaning agents commercially available. These As a rule, agents are not obtained through a spray drying process, but through Mixing, granulation and compacting processes in which high temperatures are avoided become. Because of the relatively low temperatures, the removal of water is through the starting substances are introduced, relatively lengthy. In many cases the Granulation requires a subsequent drying step.

Another problem lies in the poorer solubility of the relatively heavily compacted ones Particles. In particular, recipes with a high proportion of alkoxylated fatty alcohols are often afflicted with this problem. An improvement in solubility can be achieved if alkyl polyglycosides are incorporated into the granules. Incorporation of the However, alkyl polyglycosides are problematic because they do not have spray drying processes can be processed and the resulting particles have a high stickiness. The use of alkyl polyglycosides as a paste also results in the granulation particularly sticky in the case of granules with a high proportion of alkylbenzenesulfonate Products.

The processed polyglycoside pastes have one due to their manufacturing process Water content of about 50 wt .-%. For the production of dry, i.e. H. non-sticky, and dust-free granules, it is therefore necessary to remove the water almost completely.

The removal of water often leads to granules with fluctuating water content. Especially if the granules are to be processed into tablets, the one  the use of granulated can have fast and constant water solubility Pre-products with fluctuating water content to tablets with inconsistent Lead release speeds.

The manufacture of surfactant granules for use in detergents and cleaning agents is known from the prior art. For example, EP-A-0 859 048 describes a process for Production of surfactant granules with bulk densities above 600 g / l by Granulation of a surfactant preparation described in which solutions of Alkylbenzenesulfonate and / or alkylpolyglycoside surfactants and carrier materials in one non-surfactant solvents are simultaneously sprayed in and out through one and the same nozzle conventional dryers, preferably in the fluidized bed or in one Ring mixer dryer, dries. Polycarboxylates and inorganic carriers, especially amorphous silicates, are used.

The international patent application WO 97/03165 describes a process for the production of Sugar surfactant granules, d. H. of granules containing alkyl and / or alkenyl oligoglycosides and / or fatty acid N-alkylpolyhydroxyalkylamides. In the described Processes are aqueous pastes of the components mentioned in the presence of zeolites and / or water glasses granulated, either simultaneously or subsequently is dried. It also becomes an example of the granulation of an anhydrous mixture from an alkyl oligoglycoside and an alkoxylated fatty alcohol.

In the international patent application WO 97/09415 a manufacturing process for a non-spray dried particulate surfactant composition which discloses a Has bulk density of at least 600 g / l and a polymeric builder component and / or a soil release polymer. The granulating liquid and solid components are mixed in a granulator and the polymer is mixed with a added non-aqueous diluent during the granulation step. As not aqueous diluent is preferably an ethoxylated nonionic surfactant used.

International patent application WO 97/02338 discloses a method of manufacture of particulate surfactant compositions with a bulk density below 700 g / l. For Preparation of the disclosed surfactant composition initially becomes particulate  Starting material that does not contain at least 10% by weight of a component with a bulk density has over 600 g / l and which is not a surfactant compound with a liquid binder in mixed in a granulator and then granulated. The particulate The starting material contains a builder surfactant or a precursor thereof contain particulate starting material and / or in the binder.

International patent application WO 97/22685 discloses a process for the production of particulate detergent and cleaning compositions with bulk densities between 300 and 1300 g / l. In the process disclosed, particulates become Starting material mixed with the addition of a liquid binder and partially granulated. The partially granulated mixture is transferred to a low shear granulator, further liquid binder is added and the granulation is continued until a Particulate powder with the desired bulk density has arisen. As a liquid Binders can be water, anionic surfactant, nonionic surfactant or mixtures be used from it.

European patent application 0 799 884 describes a process for the production of free-flowing particulate surfactant compositions containing alkyl polyglycosides described that a final drying step should not be necessary. To carry out the method described, a mixture of aqueous alkyl polyglycoside paste, an ethoxylated nonionic surfactant and a solid water soluble inorganic salt. The mixture obtained separates into one organic phase and a water-rich phase, the organic phase, the alkyl polyglycoside, contains ethoxylated nonionic surfactant and water, is separated. The share of individual components in the first step is selected so that in the organic phase the ratio of alkyl polyglycoside to ethoxylated nonionic surfactant within the Range from 35:65 to 65:35 and the ratio of ethoxylated nonionic surfactant to the total amount of water is within the range of 90:10 to 60:10. For Preparation of the surfactant compositions, the resulting mixture and optionally further surfactants with one or more particulate carrier materials mixed and combined into one in a conventional high-speed mixer or granulator processed particulate product.  

The methods described above have the disadvantage that they are either very are complex to carry out or to partially free-flowing products lead to poor solubility.

The present invention was based on the object of a method for producing To provide surfactant granules that do not have the disadvantages mentioned above. In particular, a method should be found which leads to granules with a good and leads to constant solubility. Furthermore, granules should be obtained that contain such Flowability show that no further drying step is required.

Surprisingly, it has been found that if you are in a two-stage Granulation process first a fine-particle compound of alkyl polyglycoside on one suitable carrier and this compound in a second step in the presence granulated of a liquid surfactant and optionally further detergent components, free-flowing granules with good solubility are obtained without a drying step.

The present invention accordingly relates to a process for the production of surfactant granules containing nonionic surfactants and further detergent components, in which

• A) in a first process step sugar surfactants in the presence of water-soluble Carrier materials are processed into a compound and
• B) the compounds obtained in A are mixed with a non-aqueous solvent and the mixture, and optionally other detergent components, in itself be granulated in a known manner.

The sugar surfactants that can be used in process step A come especially the alkyl and alkenyl oliglycosides and polyhydroxy fatty acid amides.

The alkyl and alkenyl oliglycosides have the general formula

R ¹ O (G) _x (I)

in which R ^{1 is} a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched alkyl or alkenyl radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 carbon atoms , preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Polyhydroxy fatty acid amides which can be used are those having the formula (II).

in the R ² CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ³ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.

The polyhydroxy fatty acid amides are known substances which are customary by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a Fatty acid alkyl esters or a fatty acid chloride can be obtained. With regard to the Processes for their preparation are based on US Pat. Nos. 1,985,424, US-A- 2,016,962 and US-A-2,703,798 and International Patent Application WO-A-92/06984 referred. The polyhydroxy fatty acid amides are preferably derived from reducing agents Sugars with 5 or 6 carbon atoms, especially from the glucose.

The sugar surfactants can be in the form of aqueous solutions, such as those from the Manufacturing processes are obtained, used. Other forms of use are Granules, the production process of which is described in WO 97/03165, or steam-dried products which, according to the process described in WO 95/14519, can be obtained.

The carrier materials used in the first process step are preferred Water glass or water-soluble detergent builders, such as. B. layered silicates or organic Polymers.  

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, are suitable as water glasses call. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for × 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.

Usable organic carrier materials are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function. For example, these are  Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10,000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special  copolymers of acrylic acid with maleic acid, 50 to 90 % By weight of acrylic acid and 50 to 10% by weight of maleic acid. Your molecular weight, based on free acids, is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used. The amount of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example in EP-B-727448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol Derivatives or according to DE-C-42 21 381 as monomers salts of acrylic acid and 2- Contain alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins  higher molar masses in the range from 2000 to 30,000 g / mol. A preferred dextrin is in the British patent application 94 19 091 described.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, preferably used in the form of its sodium or magnesium salts. Also preferred in this context are also glycerol disuccinates and glycerol trisuccinates as they are for example in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP-A-0 150 930 and the Japanese patent application JP 93/339896 can be described. Suitable amounts are those containing zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups. Such cobuilders will described for example in international patent application WO 95/20029.

Other suitable carrier materials are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those in the international patent application WO-A-93/08251 or their Manufactured, for example, in international patent application WO-A-93/16110  is described. Oxidized oligosaccharides according to the German patent application DE 196 00 018.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, of which in the German Patent application DE-A-195 40 086 discloses that in addition to cobuilder properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups, for example as in European patent application EP-A- 0 280 223 can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkariphosphonates. Among the Hydroxyalkanephosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt the DTPMP. Preferred as a builder from the class of phosphonates HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the means too Contain bleach, be preferred, aminoalkanephosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth ions train as cobuilders.  

In the first process step A, compounds with a particle size of are preferred maximum 1 mm, especially maximum 0.8 mm and especially maximum 0.4 mm receive. In the event that coarser particles are formed, these can be in a the first process step, grind the downstream mill and adjust it to the desired one Particle size are brought.

The first process step is preferably carried out in a conventional fluidized bed granulation and / or steam drying system carried out.

In the second method step B, the compounds obtained in the first step A are included mixed a non-aqueous solvent, the mixture and optionally further Detergent ingredients granulated in a conventional manner.

Those compounds which are preferably used as non-aqueous solvents are: at a temperature of about 80 ° C, preferably at 40 ° C and particularly preferably at Are liquid at room temperature and also have washing-active properties. Liquid nonionic surfactants are particularly preferably used.

It has proven to be suitable for carrying out the method according to the invention Compounds first to be dissolved or dissolved in the liquid nonionic surfactants suspend. In this step, other, usually in Detergent granules contained ingredients are added.

The liquid nonionic surfactant preferably used as solvent in step B is preferably a fatty alcohol alkoxylate. Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear, are particularly suitable and may contain methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ alcohols with 7 EO, C ₁₃ -C ₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ - alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ - C ₁₄ alcohol with 3 EO and C ₁₂ -C ₁₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The granulation can be found in a wide variety of industries in the detergent and cleaning agent industries usually used apparatus can be carried out. For example, it is possible to use the rounders commonly used in pharmacy. In such turntable devices the residence time of the granules is usually less than 20 seconds. Also conventional mixers and mixing granulators are suitable for granulation. As a mixer can use both high-intensity mixers ("high-shear mixers") and normal mixers can be used with lower circulation speeds. Suitable mixers are For example, Eirich® mixers of the R or RV series (trademark of the machine factory Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark the Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (Trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim). In all mixed types and fillets the particles are built up by liquid bridge bonding non-aqueous binders. The residence times of the granules in the mixers are in the range of less than 60 seconds, the dwell time also depending on the rotational speed of the Mixer depends. Here, the dwell times decrease accordingly, the faster the Mixer is running. The residence times of the granules in the mixer / rounder are preferably less than a minute, preferably less than 15 seconds. In slow running mixers, e.g. B. a Lödige KM, dwell times of up to 20 minutes are set, whereby Residence times below 10 minutes are preferred because of the economics of the process.

In the press agglomeration process, the surfactant-containing granules are under pressure and compressed under the influence of shear forces and homogenized and then discharged form-giving from the apparatus. The most technically significant Press agglomeration processes are extrusion, roller compaction, pelleting  and tableting. In the context of the present invention preferably for the production of Press agglomerating processes containing surfactant-containing granules are extrusion Roll compacting and pelleting.

After completion of the granulation, a dry product is obtained that no other Drying step must be subjected.

The granules obtained can further increase their processability and meterability improve, be powdered with an oil absorption component. Through this final powdering step with a finely divided component Liquids set on the surface of the granules, so that the granules are stored cannot clump together. The oil absorption component should have an oil absorption capacity of at least 20 g / 100 g, more suitable at least 50 g / 100 g, preferably at least 80 g / 100 g, particularly preferably at least 120 g / 100 g and in particular at least 140 g / 100 g exhibit.

The oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, the British standard methods BS1795 and BS3483: Part B7: 1982 exist, both of which refer to the ISO 787/5 standard. In the test methods, a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93 gcm ^-3 ) from a burette is added dropwise. After each addition, the powder is thoroughly mixed with the oil using a spatula, the addition of oil being continued until a paste of smooth consistency is obtained. This paste should flow or run without crumbling. The oil absorption capacity is now the amount of the added oil, based on 100 g of absorbent, and is given in ml / 100 g or g1100 g, conversions about the density of the linseed oil being possible without any problems.

The oil absorption component preferably has the smallest possible mean Particle size, since the active surface increases with decreasing particle size. Preferred Detergent tablets contain one component with one Oil absorption capacity of at least 20 g / 100 g, which has an average particle size of below 50 microns, preferably less than 20 microns and in particular less than 10 microns.  

A large number of substances are suitable as an oil absorption component. There is a big one Number of both inorganic and organic substances, which are a large enough Have oil absorption capacity. Examples are finely divided substances that are produced by precipitation won be called. For example, silicates, aluminosilicates, Calcium silicates, magnesium silicates and calcium carbonate use. But also diatomaceous earth (Diatomaceous earth) and finely divided cellulose fibers or derivatives thereof are included in the present invention can be used. Preferred detergent tablets, are characterized in that the component contained in them with a Oil absorption capacity of at least 20 g / 100 g is selected from silicates and / or Aluminosilicates, in particular from the group of silicas and / or zeolites. Here For example, finely divided zeolites can be used, but also pyrogenic silicas (Aerosil®) or silicas that were obtained by precipitation.

Further surfactants, in particular, can be incorporated into the surfactant granules as further constituents anionic surfactants and builder substances can be incorporated.

In a preferred embodiment, the other components in the second Process step incorporated as a spray-dried powder. Temperature sensitive or Water sensitive components can be added separately.

All builders suitable for detergents and cleaning agents can be used as builders that have a sufficiently large inner surface to the nonionic surfactant to be able to record. Examples of these are zeolites, amorphous silicates, soda, phosphates and mixtures thereof, zeolite being preferred.

Fine zeolite can be, for example, finely crystalline, synthetic and bound water containing zeolite, such as zeolite A, zeolite P and mixtures of A and P can be used. Zeolite MAP® (commercial product of Crosfield).

As further preferred and particularly suitable zeolites are zeolites from To name faujasite type. The mineral faujasite belongs to the zeolites X and Y. the faujasite types within the zeolite structure group 4, which are characterized by the double Subunit D6R is marked (compare Donald W. Breck: "Zeolite Molecular  Sieves ", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92) In addition to the faujasite types mentioned, zeolite structure group 4 also includes the minerals Chabazit and Gmelinit as well as the synthetic zeolites R (Chabazit-Typ), S (Gmelinit-Typ), L and ZK-5. The latter two synthetic zeolites have no mineral Analogues.

Faujasite-type zeolites are composed of β-cages which are linked tetrahedrally via D6R subunits, the β-cages being arranged in the diamond in a manner similar to the carbon atoms. The three-dimensional network of the zeolites of the faujasite type used in the process according to the invention has pores of 2, 2 and 7.4 Å, the unit cell also contains 8 cavities with a diameter of approx. 13 Å and can be represented by the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) 106] .264 H ₂ O. The network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).

In the context of the present invention, the term “zeolite of the faujasite type” denotes all three zeolites that form the faujasite subgroup of zeolite structure group 4. Next According to the invention, zeolite X also includes zeolite Y and faujasite and mixtures of these compounds can be used according to the invention, the pure zeolite X being preferred. Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites then, which do not necessarily have to belong to the zeolite structure group 4, are inventive can be used according to, the advantages of the method according to the invention being particularly clear Lich emerge when at least 50 wt .-% of zeolites zeolites of the faujasite type are.

The aluminum silicates that are used in the process according to the invention are com commercially available, and the methods for their representation are in standard monographs wrote.

Examples of commercially available X-type zeolites can be described by the following formulas:

Na ₈₆ [AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

K ₈₆ [AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ) .x H ₂ O,

Sr ₂₁ Ba ₂₂ [AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .x H ₂ O,

in which x can have values between 0 and 276 and the pore sizes from 8.0 to 8.4 Å exhibit.

A co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which is available from CONDEA Augusts SpA under the brand name VEGOBOND AX, is commercially available and can preferably be used in the process according to the invention ® is distributed and by the formula

n Na ₂ O. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described.

Y-type zeolites are also commercially available and can be expressed, for example, by the formulas

Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] .x H ₂ O,

K ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] .x H ₂ O,

in which x stands for numbers between 0 and 276 and have a pore size of 8.0 Å, describe.

The particle sizes of the zeolites from Fauja used in the process according to the invention The sit type is in the range from 0.1 to 100 μm, preferably between 0.5 and 50 μm  and in particular between 1 and 30 µm, each with standard particle size determination methods measured.

In addition to the nonionic surfactants used according to the invention, the agents according to the invention can also contain anionic surfactants, such as, for. B. C ₈ -C ₂₂ alkyl sulfates, C ₈ -C ₂₂ alkane sulfonates, C ₈ -C ₂₂ olefin sulfonates, C ₈ -C ₂₂ alkyl benzene sulfonates, C ₈ -C ₂₂ fatty acid ether sulfates, C ₈ -C ₂₂ fatty acid ester sulfonates , sulfated fatty acid glycerol esters, 2,3-C ₈ -C ₂₂ alkyl sulfates, salts, monoesters and / or diesters of alkyl sulfosuccinic acid (sulfosuccinates), sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, fatty acid soaps or their mixtures.

Furthermore, the agents according to the invention can all usually be found in washing and cleaning agents contain agents, such as inorganic salts, bleaches, Bleach activators, graying inhibitors, foam inhibitors, salts of polyphosphonic acid ren, optical brighteners, enzymes or mixtures thereof.

The granules produced according to the invention can either be used alone Detergent components are used or with other particles that further Detergent components contain mixed and packaged.

In a preferred embodiment, the granules are mixed with other Detergent components mixed and pressed into detergent tablets.  

Examples

First, in the first process step, a sugar surfactant compound with the one in Table 1 represented composition in a fluidized bed granulation plant by atomization a 50% alkyl polyglycoside paste and a 40% Sokalan® solution (acrylic acid Maleic acid copolymer, commercial product from BASF AG, Ludwigshafen). The The product obtained was then in a mortar mill to a particle size of grind a maximum of 0.1 mm.

In the next granulation step, a powder obtained by spray drying with the composition shown in Table 2, C ₁₂ -C ₁₈ alkyl sulfate and sodium citrate in the amounts shown in Table 3 was placed in a 130 l Lödige mixer. A mixture of nonionic surfactant and the compound produced in the first process step was added in the amounts shown in Table 3 and granulated. At the end of the granulation, 3% Wessalith® XD (zeolite, commercial product from Degussa AG, Hanau) was powdered.

In Comparative Example 1, the powders were mixed with a mixture of nonionic surfactant and Granulated glycerin, in comparative example 2 only nonionic surfactant was used. The obtained granules were sieved between 0.6 and 1.6 mm. The proportion of granules, which has a particle size between 0.6 and 1.6 mm is in Table 4 as good grain designated. It was not necessary to dry the granules obtained.

The solubility of the products was examined in the so-called L test. In addition, 8 g Substance in 1000 ml of water with a hardness of 16 ° dH at 30 ° C and with a Propeller stirrer at 800 rpm, stirred for 1.5 minutes. The undissolved solids were sieved with a sieve with a mesh size of 0.2 mm. The backlog was up to Constant weight dried and weighed. The test results are in Table 4 shown.  

Table 1

Composition of the APG compound in%

Table 2

Composition of the tower powder in%

Table 3

Granulation batches in%, 8 kg total amount

Table 4

Granulate data

The results shown in Table 4 show that the proportion of good grain and Bulk density of the granules produced according to the invention and the granules from Comparative tests are in similar areas. The solubility of the invention However, the granules produced are significantly better than those from the comparative examples.

Claims (10)

1. A process for the preparation of surfactant granules containing nonionic surfactants, wherein

• A) in a first process step sugar surfactants are processed into a compound in the presence of water-soluble carrier materials and
• B) the compounds obtained in A are mixed with a non-aqueous solvent and the mixture, and optionally further detergent constituents, are granulated in a manner known per se.

2. The method according to claim 1, characterized in that the sugar surfactants are selected from the group of the alkyl and alkenyl oligoglycosides of the formula (I),
R ¹ O (G) _x (I)
in which R ^{1 is} a primary straight-chain or methyl-branched, in particular methyl-branched alkyl or alkenyl radical having 8 to 22, preferably 12 to 18, carbon atoms,
G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose, and
x for a number between 1 and 10; preferably between 1.2 to 1.4,
or the polyhydroxy fatty acid amides of the formula (II),
in which R ² CO represents an aliphatic acyl radical having 6 to 22 carbon atoms,
R ^{3 represents} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and
[Z] stand for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. 3. The method according to any one of claims 1 or 2, characterized in that the water-soluble carrier materials are selected from the group consisting of Water glasses, layered silicates or organic polymers.   4. The method according to any one of claims 1 to 3, characterized in that the in Process step A produced compounds a maximum particle size of 1 mm, preferably of at most 0.8 mm and in particular of at most 0.4 mm exhibit. 5. The method according to any one of claims 1 to 4, characterized in that non-ionic surfactant, preferably a C ₈ -C ₁₈ fatty alcohol alkoxylate having 1 to 12 alkoxy groups per molecule, is used in step B as the non-aqueous solvent. 6. The method according to any one of claims 1 to 5, characterized in that the obtained granules are powdered with a component that a Oil absorption capacity ≧ 20 g / 100 g. 7. The method according to any one of claims 1 to 6, characterized in that the obtained granules are not subjected to a drying step. 8. The method according to any one of claims 1 to 7, as further detergent ingredients further surfactants, especially anionic surfactants, and builder substances, inorganic salts, bleaching agents, bleach activators, graying inhibitors, Foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes or their mixtures are included. 9. The method according to claim 8, characterized in that the further Detergent ingredients at least partially in the form of a spray dried powder be used. 10. Use of the surfactant granules, produced according to one of claims 1 to 9, for Manufacture of detergent tablets.