EP1274826B1 - Method for producing non-ionic tenside granulates - Google Patents

Abstract

Surfactant granules are made by the process comprising the steps of (1) mixing an aqueous nonionic surfactant paste and an aqueous solution of an organic polymeric carrier; (2) simultaneously granulating and drying the mixture from step (1) in a fluidized bed to form a granulated nonionic surfactant. The surfactant granules are dust-free, flowable, storage-stable, show no tendency toward clumping and are readily soluble in cold water.

Description

Field of the invention

The invention relates to surfactant granules which are obtained by granulating and simultaneously drying aqueous pastes of nonionic surfactants in the presence of organic polymeric carriers, a process for their preparation and their use in surface-active preparations.

State of the art

Nonionic surfactants, such as, for example, alkyl oligoglucosides, are distinguished by excellent detergent properties and high ecotoxicological compatibility. For this reason, these classes of nonionic surfactants are becoming increasingly important. So far, they are usually used in liquid formulations, such as dishwashing or hair shampoos, so there is also a great market need for solid, anhydrous forms of sale, which can be incorporated, for example, in solid detergents and cosmetics.

Detergents include not only the powder detergents, but especially the particulate detergents, such as To understand detergent tablets. In particular, with the latter, it has been found that through the use of solid nonionic surfactant granules, migration and penetration of the nonionic surfactant into other components of the detergent tablet, e.g. into the so-called "disintegrants" ingredient, while in conventional manufacturing in which the nonionic surfactant is spread over the entire detergent powder by jetting before it is compressed into tablets, a penetration of the nonionic surfactant into the " Blasting agent "comes, which then loses its effectiveness, so that then the rapid disintegration of the tablet is delayed or completely prevented at the beginning of the washing process.

In cosmetic products, on the other hand, the advantage of using solid nonionic surfactant granules is that these anhydrous products are inert even when stored without preservatives against fungi, yeasts and bacteria and that this microbiological stability is also achieved when the solid anhydrous surfactant has a neutral pH Value.
This accommodates the consumer, who has a need for cosmetic products that are free of preservatives.

For the manufacturers of detergents and cosmetic products, the solid, non-ionic anhydrous surfactants can only be used if these products are used in the manufacture of detergents. and cosmetic products are easy to work with. It is therefore essential that the solid, anhydrous nonionic surfactants have a good flowability, so that they can be traded in silo cars or "big bags". Furthermore, the solid, water-free nonionic surfactants must also be dust-free, so that when they are processed no risk of dust explosion and the processor no risk of adverse health effects, eg by inhalation of surfactant dusts exists.

The drying of liquid surfactant preparations is generally carried out by conventional spray drying, in which the aqueous surfactant paste is sprayed at the head of a spray tower in the form of fine droplets, which hot drying gases are counteracted. For example, German Patent Application DE 4102745 A1 (Henkel) discloses a process in which fatty alcohol sulfate pastes are added to a small amount of from 1 to 5% by weight of alkyl glucosides and subjected to conventional spray drying. However, the process can only be carried out in the presence of a large amount of inorganic salts. German patent application DE 4139551 A1 (Henkel) proposes to spray pastes of alkyl sulfates and alkyl glucosides, which, however, may contain not more than 50% by weight of the sugar surfactant, in the presence of mixtures of soda and zeolites. Here, however, only compounds are obtained which have a low surfactant concentration and an insufficient bulk density. Finally, International Patent Application WO 95/14519 (Henkel) reports subjecting surfactant pastes to superheated steam drying. However, this method is technically very complicated.

EP-A-859048 describes nonionic surfactant granules and a process for their preparation. In this case, alkylpolyglycoside surfactants and inorganic and / or organic support materials are atomized simultaneously, the organic support material being exclusively polycarboxylates, preferably acrylic acid / maleic acid copolymers. German patent application DE-A-19824742 describes a process for the production of APG-containing granules containing granulation components by spraying an aqueous mixture of these components onto a solid mixture consisting of customary builders. The granulation component contains acrylic acid-maleic acid copolymer in addition to numerous inorganic compounds.
WO-A-9319155 discloses a process for producing free-flowing detergent granules . Here, aqueous alkyl and / or alkenyl oligoglycoside pastes are granulated in addition to other anionic and / or nonionic surfactants and / or conventional detergent ingredients containing starch and other inorganic compounds as solids. DE-C-19710153 discloses the use of surfactant granules containing nonionic surfactants in cosmetics.

The complex object of the invention was thus to provide a simple process for the preparation of nonionic surfactant granules, in which the presence of inorganic compounds, such as soda, zeolites and inorganic salts, can be dispensed with. In addition, granules should be available by this method, which are characterized by high surfactant contents, high bulk densities and good color quality and are dust-free, free-flowing and storage stable. Furthermore, these nonionic surfactant granules should dissolve rapidly in water even at low temperatures, for example at 20 ° C.

Description of the invention

The invention relates to surfactant granules, obtainable by granulating aqueous pastes of nonionic surfactants in the presence of organic polymeric support materials (also referred to as organic polymer hereinafter) and dried at the same time.

Another object of the invention relates to a process for the preparation of surfactant granules, in which granulating aqueous pastes of nonionic surfactants in the presence of organic polymeric support materials and dried at the same time.

Surprisingly, it has been found that nonionic surfactant granules are obtained using organic polymeric support materials without the addition of inorganic compounds, such as, for example, zeolites or soda. Particularly surprising is the finding that it has proved to be even more advantageous not to granulate the aqueous nonionic surfactant pastes together with the solid organic polymers in a fluidized bed and dry at the same time, but first to dissolve the organic polymers in the aqueous surfactant paste and then the aqueous mixture of surfactant and polymer together in a fluidized bed to granulate and dry. In this case, the organic polymer is not only a carrier material but also a structural improver. The surfactant granules according to the invention are distinguished by an unexpectedly high apparent density in the range from 600 to 1000 g / l. The granules are externally dry even in the case of a residual water content of up to 20 wt .-%, so that a subsequent drying is not required. They are dust-free, free-flowing, storage-stable, show no tendency to clumping and are also soluble in cold water easily and practically without residue. In addition, they have an excellent color quality.

Nonionic surfactants

Suitable nonionic surfactants are alkyl and alkenyl oligoglycosides, fatty acid N-alkylpolyhydroxyalkylamides, alcohol ethoxylates, alkoxylated carboxylic acid esters, preferably alkyl and alkenyl oligoglycosides.

Alkyl and / or alkenyl oligoglycosides

Alkyl and / or alkenyl oligoglycosides are known nonionic surfactants which follow formula (I),

R ¹ Q- [G] _p (I)

in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained by the relevant methods of preparative organic chemistry. Representing the extensive Let's look at the review article by Biermann et al. in Starchl Strength 45, 281 (1993) , B. Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in SÖFW Journal Heft 8, 598 (1995) .

The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (I) indicates the degree of oligomerization (DP), ie the distribution of monoglycerides and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and here especially If p = 1 to 6 can be assumed, the value p for a given alkyloligoglycoside is an analytically determined arithmetic quantity, which usually represents a fractional number. Preference is given to using alkyl and / or alkenyl oligoglycosides having an average degree of oligomerization p of from 1.1 to 3.0. From an application point of view, those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.6 are preferred. The alkyl or alkenyl radical R ¹ can be derived from primary alcohols having 4 to 11, preferably 8 to 10 carbon atoms. Typical examples are butanol, caproic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol, and technical mixtures thereof, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the hydrogenation of aldehydes from Roelen's oxosynthesis. Preference is given to alkyl oligoglucosides of the chain length C ₈ -C ₁₀ (DP = 1 to 3), which are obtained as a feedstock in the distillative separation of C ₈ -C ₁₈ technical _grade coconut fatty alcohol and having a fraction of less than 6% by weight C ₁₂ - Alcohol may be contaminated as well as alkyl oligoglucosides based on technical C _9/11 , C _12/13 , C _12/15 and C _14/15 oxo alcohols (DP = 1 to 3). Particularly preferred are the technical Oxoalkohole the company Shell, which are marketed under the name Dobanol® or Neodol®. The alkyl or alkenyl radical R ¹ can also be derived from primary alcohols having 12 to 22, preferably 12 to 18 carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol, and technical mixtures thereof which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated _{C12 / 14} coconut or palm kernel alcohol or C _16/18 fatty alcohol from coconut palm kernel oil or palm oil with a DP 1 to 3

Fatty acid-N-alkylpolvhvdroxyalkylamide

in der R²CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R³ für einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 12 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Fettsäure-N-alkylpolyhydroxyalkylamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Hinsichtlich der Verfahren zu ihrer Herstellung sei auf die US-Patentschriften US 1,985,424, US 2,016,962 und US 2,703,798 sowie die internationale Patentanmeldung WO 92/06984 verwiesen. Eine Übersicht zu diesem Thema von H. Kelkenberg findet sich in Tens.Surf.Deterg. 25, 8 (1988). Fatty acid N-alkylpolyhydroxyalkylamides are nonionic surfactants which follow formula (1),

in which R ² CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{3 is} an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. The fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. With regard to the processes for their preparation, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO 92/06984 . An overview of this topic by H. Kelkenberg can be found in Tens.Surf.Deterg. 25, 8 (1988).

Preferably, the fatty acid N-alkylpolyhydroxyalkylamides are derived from reducing sugars having 5 or 6 carbon atoms, especially glucose. The preferred fatty acid N-alkylpolyhydroxyalkylamides are therefore fatty acid N-alkylglucamides as represented by the formula (II) :

Preferably used as fatty acid N-alkylpolyhydroxyalkylamides are glucamides of the formula (II) in which R ^{3 is} an alkyl group and R ² CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, Oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures. Particular preference is given to fatty acid N-alkylglucamides of the formula (II) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C _12/14 coconut fatty acid or a corresponding derivative. Furthermore, the polyhydroxyalkylamides can also be derived from maltose and palatinose.
Also, the use of the fatty acid N-alkylpolyhydroxyalkylamide is the subject of a variety of publications. European patent application EP 0285768 A1 (Hüls), for example, discloses its use as a thickener. French patent application FR 1580491 A (Henkel) describes aqueous detergent mixtures based on sulfates and / or sulfonates, nonionic surfactants and optionally soaps containing fatty acid N-alkylglucamides as foam regulators. Mixtures of short- and longer-chain glucamides are described in German Patent DE 4400632 C1 (Henkel). In the German Offenlegungsschriften DE 4326959 A1 and DE 4309567 A1 (Henkel) is also reported on the use of glucamides with longer alkyl radicals than pseudoceramides in skin care products as well as on combinations of glucamides with protein hydrolysates and cationic surfactants in hair care products. The subject of international patent applications WO 92/06153, WO 92/06156, WO 92/06157, WO 92/06158, WO 92/06159 and WO 92/06160 (Procter & Gamble) are mixtures of fatty acid N-alkylglucamides with anionic surfactants, Surfactants having sulfate and / or sulfonate structure, ether carboxylic acids, ether sulfates, methyl ester sulfonates and nonionic surfactants. The use of these substances in a wide variety of detergents, dishwashing detergents and cleaners is described in International Patent Applications WO 92/06152, WO 92/06154, WO 92/06155, WO 92/06161, WO 92/06162, WO 92/06164, WO 92 / 06170, WO 92/06171 and WO 92/06172 (Procter & Gamble).

alcohol ethoxylates

Alcohol ethoxylates are referred to as fatty alcohol or oxo alcohol ethoxylates and preferably follow the formula (III),

R ⁴ O (CH ₂ CH ₂ O) n H (III)

in which R ^{4 is} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n is a number from 1 to 50. Typical examples are the adducts of an average of 1 to 50, preferably 5 to 40 and especially 10 to 25 moles of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, for example, in the high pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from the Roelen oxo synthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Preferred are adducts of 10 to 40 moles of ethylene oxide with technical fatty alcohols having 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty alcohol.

Alkoxylated carboxylic acid esters

Alkoxylated carboxylic acid esters are known in the art. For example, such alkoxylated carboxylic acid esters are obtainable by esterification of alkoxylated carboxylic acids with alcohols. However, for the purposes of the present invention, the compounds are prepared by reacting carboxylic acid esters with alkylene oxides using catalysts, in particular using calcined hydrotalcite according to the German Offenlegungsschrift DE 3914131 A, which provide compounds with a limited Homolgenverteilung. Both carbonic acid esters of monohydric alcohols and of polyhydric alcohols can be alkoxylated by this process. Preferred according to the present invention are alkoxylated carboxylic acid esters of monohydric alcohols which follow the general formula (IV) ,

R ⁵ CO (OAlk) _n OR ⁶ (IV)

wherein R ^{5 is} CO for an aliphatic acyl radical derived from a carboxylic acid, AlkO for alkylene oxide and R ^{6 is} an aliphatic alkyl radical derived from a monohydric aliphatic alcohol. Especially suitable are alkoxylated carboxylic acid esters of the formula (IV) in which R ⁵ CO is an aliphatic acyl radical having 6 to 30, preferably 6 to 22 and in particular 10 to 18 carbon atoms, AlkO is a CH ₂ CH ₂ O-, CHCH ₃ CH ₂ O- and / or CH ₂ -CHCH ₃ O radical, n average for numbers from 1 to 30, preferably 5 to 20 and in particular 10 to 15 and R ⁶ for an aliphatic alkyl radical having 1 to 4 and preferably 1 and / or 2 Carbon atoms.

Preferred acyl radicals are derived from carboxylic acids having 6 to 22 carbon atoms of natural or synthetic origin, especially linear, saturated and / or unsaturated fatty acids including technical mixtures thereof, as obtainable by lipolysis from animal and / or vegetable fats and oils, for example from coconut oil, palm kernel oil, palm oil, soybean oil, sunflower oil, rapeseed oil, cottonseed oil, fish oil, beef tallow and lard. Examples of such carboxylic acids are caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and / or erucic acid ,

Preferred alkyl radicals are derived from primary, aliphatic monofunctional alcohols having 1 to 4 carbon atoms, which may be saturated and / or unsaturated. Examples of suitable monoalcohols are methanol, ethanol, propanol, and butanol, especially methanol.

Alk0 represents the alkylene oxides which are reacted with the carboxylic acid esters and include ethylene oxide, propylene oxide and / or butylene oxide, preferably ethylene oxide and / or propylene oxide, especially ethylene oxide alone.

Especially suitable are alkoxylated carboxylic acid esters of the formula (IV) in which AlkO is a CH ₂ CH ₂ O radical, n is an average of from 10 to 15 and R ^{2 is} a methyl radical. Examples of such compounds are methyl lauric acid alkoxylated on average with 5, 7, 9 or 11 moles of ethylene oxide, methyl coconut oil fatty acid ester and tallow fatty acid methyl ester.

The nonionic surfactants can be used in amounts of 20 to 95, preferably 50 to 80 and in particular 60 to 70 - based on the final concentration.

Organic polymeric carrier materials

Suitable organic polymeric carrier materials are cationic, anionic, zwitterionic, amphoteric and / or nonionic organic polymers. In a preferred embodiment of the invention can be used as organic polymers polypeptides, celluloses, polyvinyl alcohols, polyvinylpyrrolidone, polycondensates, polyhydroxycarboxylic acids, polyethylene glycol, polyesters, polyurethanes and / or derivatives thereof.

Suitable organic cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethylcellulose which is obtainable under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone-vinylimidazole polymers, such as, for example, Luviquat® (BASF), Condensation products of polyglycols and amines, quaternized collagen polypeptides such as lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethylenimine, cationic silicone polymers such as amodimethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretine® / Sandoz), copolymers of acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), polyaminopolyamides, as described, for example, in FR 2252840 A and their crosslinked water-soluble polymers, cationic chitin derivatives such as, for example, quaternized Ch itosan, optionally microcrystalline distributed, condensation products of dihaloalkylene, such as dibromobutane with bis-dialkylamines, such as bis-dimethylamino-1,3-propane, cationic guar gum, such as Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol.

Examples of suitable organic anionic, zwitterionic, amphoteric and nonionic polymeric carriers are vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, acrylamidopropyltrimethylammonium chloride / acrylate copolymers, octylacrylamide / Methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers, polyvinylpyrrolidone, Vinylpyrrolidoninyl acetate copolymers, vinylpyrrolidone / dimethylaminoethyl methacrylate / vinylcaprolactam terpolymers and optionally derivatized cellulose ethers in question. Further suitable polymers and thickeners are listed in Cosmetics & Toiletries Vol. 108, May 1993, page 95ff .

In a preferred embodiment of the invention come as organic polymeric carrier Po. polypeptides, cellulose, polyvinyl alcohols, polyvinylpyrrolidone polycondensates, polyhydroxycarboxylic acids and / or their derivatives in question.

(1) proteins

For the purposes of the invention, proteins are polypeptides based on animal protein (for example collagen) or on vegetable protein with a molecular weight of from 1,000 to 300,000, preferably 5,000 to 200,000 and in particular 10,000 to 150,000.

In a particular embodiment, water-soluble proteins are used, e.g. based on wheat protein. In this case, a molecular weight of 5,000 to 50,000 is particularly preferable. Corresponding proteins based on whey, soy, rice and silk can also be used.

Particular preference is given to using protein hydrolysates having an average molecular weight of 500 to 30,000 (for example Gluadin® WP, from Cognis GmbH). In a preferred embodiment of the invention, it is likewise possible to use anionically or cationically modified protein hydrolysates (for example Gluadin WQ, Cognis GmbH).

Polypeptides may also be prepared by known means from amino acids and their derivatives, i. from carboxylic acids having one or more amino groups in the molecule. For the purposes of the invention, the proteins or polypeptides can be prepared by linking the individual amino acids and any desired combination thereof. Glycine, alanine, serine, cysteine, phenylalanine, tyrosine, tryptophan, threonine, methionine, valine, proline, leucine, isoleucine, lysine, arginine, histidine, L-aspartic acid, asparagine, glutamic acid, glutamine and derivatives thereof are used as amino acids, for example. For example, polyethylene glutamate) in question, which contain at least one COOH and at least one amino group after derivatization. Polyasparaginate (for example with MG 20,000 (Donlar) or with MG 2,000 - 3,000 (Bayer) are preferably suitable.

(2) polysaccharides and / or their derivatives

The polysaccharides are cellulose and derivatives thereof, in particular xanthan gum, guar guar (eg guar hydroxypropyltrimethylammonium chloride, Cosmedia Guar C 261, Cognis GmbH, Guarmehl, Cosmedia Guar U, Cognis GmbH), agar-agar, alginates and Tylose , Carboxymethylcellulose and hydroxyethylcellulose, dextrin, cyclodextrin, carboxymethyl dextran and their derivatives.

Chitin is to be understood as meaning amino sugar-containing polysaccharides of the general formula (C ₈ H ₁₃ NO ₅ ) _x , which usually have molecular weights in the order of an average of 30,000 to 5,000,000 daltons. Chitins consist of chains of β-1,4-glycosidically linked N-acetyl-D-glucosamine residues. Particularly preferred is the use of chitin having a molecular weight of 50,000 to 2,000,000 daltons.

Chitosans are, inter alia, biopolymers and are counted among the group of hydrocolloids. Chemically, they are partially deacetylated chitins, ie amino sugar-containing polysaccharides of different molecular weight, containing the following - idealized - monomer unit:

unlike most hydrocolloids, which are negatively charged at biological pH levels, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products as well as pharmaceuticals Preparations used (see Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pp. 231-232) . Surveys on this topic are also for example by B. Gesslein et al. in HAPPI 27, 57 (1990), O. Skaugrud in Drug Cosm. 148 , 24 (1991) and E. Onsoyen et al. in Soaps Oils-Fette-Wachse 117 , 633 (1991) . For the production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available as cheap raw materials in large quantities. The chitin is thereby used in a process first described by Hackmann et al. has been described, usually initially deproteinized by the addition of bases, demineralized by the addition of mineral acids and finally deacetylated by the addition of strong bases, wherein the molecular weights may be distributed over a broad spectrum. Appropriate Ver drive are for example made of macromol. Chem. 177, 3589 (1976) or French patent application FR 2701266 A. Preferably, such types are used as disclosed in German patent applications DE 4442987 A1 and DE 19537001 A1 (Henkel) and having an average molecular weight of 10,000 to 5,000,000 daltons, in particular 10,000 to 500,000 or 800,000 to 1,200,000 daltons, and or a Brookfield viscosity (1% by weight in glycolic acid) below 5,000 mPas, a degree of deacetylation in the range of 80 to 88% and an ash content of less than 0.3% by weight. Usually, chitosans having an average molecular weight of 10,000 to 5,000,000 daltons are used, in a preferred embodiment, chitosans having an average molecular weight of 30,000 to 100,000 daltons are used, further preferred are chitosans having a molecular weight of 100,000 to 1,000,000 daltons, particularly preferred are chitosans with a molecular weight of 800,000 to 1,000,000 daltons.

In addition to chitosans as typical cationic biopolymers, anionic or nonionically derivatized chitosans, such as, for example, carboxylation, succinylation or alkoxylation products are also suitable for the purposes of the invention, as described, for example, in German Patent DE 3713099 C2 (L'Oreal) and German Pat Patent Application DE 19604180 A1 (Henkel).

(3) Polyvinyl alcohols

For the purposes of the invention, polymers have the general structure -CH ₂ CHOH-CH ₂ -CH ₂ OH-, which in small proportions (about 2%) may also contain structural units of the type -CH ₂ CHOH-CHOH-CH ₂ OH. Polyvinyl alcohols can not be obtained directly by polymerization of vinyl alcohol (H ₂ C = CH-OH), since its concentration in the tautomeric equilibrium (keto-enol tautomerism) with acetaldehyde (H ₃ C-CHO) is too low. Polyvinyl alcohols are therefore prepared mainly from polyvinyl acetates via polymer-analogous reactions such as hydrolysis, but in particular technically by alkaline catalyzed transesterification with alcohols (preferably methanol) in solution. In the context of the invention are preferably polyvinyl alcohols, which are offered as white-yellowish powder or granules with degrees of polymerization in the range of preferably 500 to 2500 (molecular weights of about 20 000-100 000 g / mol) have degrees of hydrolysis of 98 to 99 or 87 to 89 mol%, so still contain a residual content of acetyl groups. Suitable products preferably have a molecular weight of 5,000 to 50,000 and especially 10,000 to 30,000.

(4) polyvinylpyrrolidones

Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones) are prepared by free-radical polymerization of 1-vinylpyrrolidone by methods of bulk, solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators and usually in the presence of aliphatic Amines that prevent decomposition of the monomer in acidic medium. The ionic polymerization of the monomer provides only low molecular weight products.

Preferably, polyvinylpyrrolidones having molecular weights in the range of 2,500 to 75,000, more preferably 5,000 to 60,000 and in particular in the range of 20,000 to 50,000 g / mol in question.

(5) polycondensates

Suitable polypeptides are copolymers of polypeptides with dicarboxylic acids (for example poly-β-alanine / glutaric acid copolymer), vinylpyrrolidone and vinyl acetates, polyols and poly (meth) acrylates.

(6) polyhydroxycarboxylic acids

Copolymers of vinyl alcohol and (meth) acrylic acids can also be used as polyhydroxycarboxylic acids. A particular embodiment is polyhydroxycarboxylic acids, which are prepared by polycondensation of polyhydroxy acids such as tartaric acid, citric acid, malic acid and mixtures thereof.

The organic polymeric support materials can be used in amounts of 0.1 to 50, preferably 1 to 30 and in particular 5 to 20 - based on the final concentration.

Granulation in the fluidized bed

A fluidized-bed or SKET granulation means granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed. The nonionic surfactants may preferably be introduced into the fluidized bed simultaneously or successively via one or more nozzles in the form of aqueous pastes. Preferably used fluidized bed plants have bottom plates with dimensions of 0.4 to 5 m. Preferably, the SKET granulation is carried out at fluidized air velocities in the range of 1 to 8 m / s. The discharge of the granules from the fluidized bed is preferably carried out via a size classification of the granules. The classification can be carried out, for example, by means of a sieve device or by a countercurrent air stream (classifier air), which is regulated in such a way that only particles above a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. Usually, the incoming air is composed of the heated or unheated classifier air and the heated bottom air. The soil air temperature is between 60 and 400, preferably 60 and 350 ° C. Advantageously, an organic polymeric carrier material or a SKET granulate from an earlier experimental batch is initially introduced as the starting mass of the SKET granulation. In the fluidized bed, the water evaporates from the surfactant paste, which in addition the surfactant also contains the polymer to give dried to dried seeds, which are coated with other amounts of surfactant / polymer mixture, granulated and dried again at the same time. The result is a surfactant / polymer grain with a surfactant gradient over the com, which is particularly soluble in water. The granulation with simultaneous drying can be carried out without the addition of inorganic salts, such as zeolite and soda.

In a preferred embodiment of the invention, these surfactant granules have a particle size distribution between 0.02 and 2.0 and in particular between 0.2 and 1.6 mm. In a further preferred embodiment of the invention, at least 70, particularly preferably 75 and in particular 85% by weight of the granules consist of round grains.

Preferred embodiments of the granulation

The inventive method can be carried out in two embodiments - both in the mixer and in the fluidized bed. Preferably, the granulation is carried out in the fluidized bed or in a fluidized bed spray tower. On the one hand, it is possible to introduce the organic polymeric carriers as crystallization seeds and to spray on a very highly concentrated, for example 30 to 65% by weight paste of a nonionic surfactant. On the other hand, an organic polymer or mixtures of various polymers - in the case that they are water-soluble - are also dissolved in the nonionic aqueous surfactant pastes or - in the case that these are water-insoluble - are mixed into a kind of "slurry" and then sprayed together or preferably granulated and simultaneously dried by counterflow of hot air.

surfactants

Although the object of the invention is directed to the production of nonionic surfactant granules, together with these surfactants it is also possible to use further anionic, nonionic, amphoteric or zwitterionic and cationic surfactants.
Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, fatty acid ether sulfates, hydroxy mixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates , Mono- and dialkylsulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acyl amino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (especially wheat-based vegetable products) and alkyl (ether) phosphates. Unless the anionic surfactants contain polyglycol ether chains, they may have a conventional, but preferably a narrow homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed or glucuronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (especially wheat-based vegetable products), polyol fatty acid esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, these may have a conventional, but preferably a narrow homolog distribution. Typical examples of cationic surfactants are quaternary ammonium compounds such as dimethyl distearyl ammonium chloride or alkyl trimethyl ammonium chloride, and ester quats, especially quaternized fatty acid trialkanolamine ester salts. Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidobetaines (such as cocoamidopropylbetaine), aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines. The surfactants mentioned are exclusively known compounds. With regard to the structure and production of these substances, reference may be made, for example, to J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, p. 54,124 or J.Falbe (ed.), "Catalysts, surfactants and Mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp. 123-217 . Typical examples of particularly suitable mild, ie particularly skin-friendly surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefinsulfonates, ethercarboxylic acids, alkyloligoglucosides, fatty acid glucamides, alkylamidobetaines, amphoacetals and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

The mixing ratio between the nonionic surfactants and the other surfactants is largely uncritical and may vary in the range of 10:90 to 90:10. Preference is given to mixtures of the inventive mixture of nonionic surfactants and organic polymer with fatty alcohol sulfates, oxoalcohol sulfates, monoglyceride sulfates, fatty acid isethionates, soaps, olefinsulfonates, acylglutamates, sarcosinates, ethercarboxylic acids and fatty alcohol polyglycol ethers in a weight ratio of 70:30 to 30:70 and in particular 60:40 to 40: 60th

In a particular embodiment of the invention, the above-described granulation of the aqueous nonionic surfactant / polymer paste in the presence of another surfactant paste from fatty alcohol sulfates, betaines, coconut monoglyceride sulfates, acyl glutamates, esterquats or mixtures thereof, with simultaneous drying is performed.

In a further embodiment of the invention, initially as described above, the granulation of the aqueous nonionic surfactant / polymer paste with simultaneous drying to the surfactant granules; Subsequently, these surfactant granules are recycled back into the fluidized bed as seed material and in the presence of another surfactant paste of fatty alcohol sulfate, betaine, Kokosmonoglyceridsutfat, Acylglutamate and / or mixtures thereof a second time granulated and dried simultaneously.

Industrial Applicability

The agents according to the invention can be used in surface-active preparations, such as, for example, cosmetic and / or pharmaceutical preparations, i.a. Hair shampoos, hair lotions, bubble baths, shower baths, mouthwashes and dentifrices, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, stick preparations, powders or ointments, cleaning preparations, preferably washing, rinsing, cleaning - And softeners and preparations for the treatment of textiles, preferably ironing aids and the like are used.

The surfactant granules according to the invention, preferably sugar surfactant granules, are free-flowing, do not agglomerate and dissolve easily in cold water. They are therefore suitable, for example, for the preparation of powder detergents and in particular for the preparation of particulate detergents such as detergent tablets, wherein the granules are preferably admixed to the tower powder and, for example. in the case of the detergent tablets, this powder mixture then pressed to the tablets.

An object of the invention therefore relates to the use of the surfactant granules according to the invention in surface-active preparations, preferably cosmetic and / or pharmaceutical preparations and detergents and cleaners and in particular solid powdery or particulate detergents and cleaners, preferably in tablet form.

The surface-active preparations may also be used as further additives mild surfactants, oil components, emulsifiers, superfatting agents, pearlescent, consistency, thickening agents, polymers, silicone compounds, fats, waxes, stabilizers, biogenic agents, Deowirkstoffe, anti-dandruff agents, film formers, swelling agents, other UV protection factors, antioxidants , Hydrotropes, preservatives, insect repellents, self-tanning agents, solubilizers, perfume oils, dyes, anti-sprouting agents, and the like.

Typical examples of suitable mild, ie particularly skin-compatible, surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, α-olefinsulfonates, ethercarboxylic acids, alkyl oligoglucosides, fatty acid glucamides, cocoamidopropylbetaine, alkylamidobetaines, cocoamidosulfebetaines and / or protein fatty acid condensates, the latter preferably based on wheat proteins.

As oil components of the required polarity are in particular Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of branched C ₆ -C ₁₃ carboxylic acids with linear C ₆ -C ₂₂ fatty alcohols, esters of linear C ₆ -C _22- fatty acids with branched alcohols, especially 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ fatty alcohols, in particular dioctyl malates, esters of linear and / or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimerdiol or trimer triol ) and / or Guerbet alcohols, liquid mono- / di- / triglyce (mixtures based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols) and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid , Esters of C ₂ -C ₁₂ dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 Hydroxylg groups, branched primary alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ -feftalkohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ -alcohols (eg Finsolv® TN), linear or branched, symmetrical or unsymmetrical dialkyl ethers having 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols into consideration.

As superfatting agents, substances such as lanolin and lecithin as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used, the latter also serving as foam stabilizers.

Suitable pearlescing waxes are, for example: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.
As consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and in addition partial glycerides, fatty acids or hydroxy fatty acids into consideration. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates.

Suitable thickening agents are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, (eg Carbopols ® 'from Goodrich or Synthalenee from Sigma), polyacrylamides, Polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or Alkyloligoglucoside and electrolytes such as sodium chloride and ammonium chloride.

Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which may be both liquid and resin-form at room temperature. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates. A detailed overview of suitable volatile silicones can also be found in Todd et al. in Cosm.Toil. 91 , 27 (1976) .

Typical examples of fats are glycerides, waxes include beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax, hydrogenated castor oils, solid fatty acid esters or microwaxes, optionally in combination with hydrophilic waxes, eg cetylstearyl alcohol or partial glycerides.

As stabilizers, metal salts of fatty acids, e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate can be used.

Biogenic active ingredients are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.

As Deowirkstoffe such as antiperspirants such as aluminum chlorohydrates come into question. These are colorless, hygroscopic crystals which easily deliquesce in the air and are formed on evaporation of aqueous aluminum chloride solutions. Aluminum chlorohydrate is used for the production of antiperspirant and deodorizing preparations and is likely to act via the partial occlusion of the sweat glands by protein and / or polysaccharide precipitation [cf. J.Soc. Cosm.Chem. 24, 281 (1973)]. For example, an aluminum chlorohydrate which conforms to the formula [Al ₂ (OH) ₅ Cl] * 2.5 H ₂ O and whose use is particularly preferred is commercially available under the name of Locron® from Hoechst AG, Frankfurt / Main, [cf. J.Pharm.Pharmacol. 26, 531 (1975) ]. In addition to the chlorohydrates, it is also possible to use aluminum hydroxylactates and acidic aluminum / zirconium salts. As further Deowirkstoffe esterase inhibitors can be added. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Dusseldorf / FRG). The substances inhibit the enzyme activity and thereby reduce the formation of odors. The cleavage of the citric acid ester is likely to release the free acid, which lowers the pH level on the skin, thereby inhibiting the enzymes. Further substances which are suitable as esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid , Adipinsäuremonoethylester, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or diethyl tartrate. Antibacterial agents that affect the bacterial flora and kill sweat-degrading bacteria or inhibit their growth may also be included in the stick formulations. Examples of these are chitosan, phenoxyethanol and chlorhexidine gluconate. 5-chloro-2- (2,4-dichlorophenoxy) phenol, which is marketed under the trade name Irgasan® by Ciba-Geigy, Basel / CH, has also proved to be particularly effective.

As anti-dandruff agents Climbazol, Octopirox® and zinc pyrithione. Typical film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or salts thereof and similar compounds.

Suitable aqueous phase swelling agents include montmoriflonites, clay minerals, pemulen and alkyl-modified carbopol types (Goodrich). Further suitable polymers or swelling agents can be reviewed by R. Lochhead in Cosm.Toil. 108 , 95 (1993) .

• 4-Aminobenzoesäurederivate, vorzugsweise 4-(Dimethylamino)benzoesäure-2-ethylhexylester, 4-(Dimethylamino)benzoesäure-2-octylester und 4-(Dimethylamino)benzoesäureamylester;
• Ester der Salicylsäure, vorzugsweise Salicylsäure-2-ethylhexylester, Salicylsäure-4-isopropylbenzylester, Salicylsäurehomomenthylester;
• Derivate des Benzophenons, vorzugsweise 2-Hydroxy-4-methoxybenzophenon, 2-Hydroxy-4-methoxy-4'-methylbenzophenon, 2,2'-Dihydroxy-4-methoxybenzophenon;
• Ester der Benzalmalonsäure, vorzugsweise 4-Methoxybenzmalonsäuredi-2-ethylhexylester;
• Triazinderivate, wie z.B. 2,4,6-Trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazin und Octyl Triazon, wie in der EP 0818450 A1 beschrieben;
• Propan-1,3-dione, wie z.B. 1-(4-tert.Butylphenyl)-3-(4'methoxyphenyl)propan-1,3-dion;
• Ketotricyclo(5.2.1.0)decan-Derivate, wie in der EP 0694521 B1 beschrieben.

Under UV sun protection factors are, for example, at room temperature, liquid or crystalline organic substances present (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat again. UV-B filters can be oil-soluble or water-soluble. Examples of oil-soluble substances are:

• 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester;
• Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate;
• Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
• Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate;
• Triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone as described in EP 0818450 A1 ;
• Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione;
• Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1 .

• 2-Phenylbenzimidazol-5-sulfonsäure und deren Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium- und Glucammoniumsalze;
• Sulfonsäurederivate von Benzophenonen, vorzugsweise 2-Hydroxy-4-methoxybenzophenon-5-sulfonsäure und ihre Salze;
• Sulfonsäurederivate des 3-Benzylidencamphers, wie z.B. 4-(2-Oxo-3-bornylidenmethyl)benzolsulfonsäure und 2-Methyl-5-(2-oxo-3-bornyliden)sulfonsäure und deren Salze.

Suitable water-soluble substances are:

• 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;
• Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
• Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

In addition to the two aforementioned groups of primary light stabilizers, it is also possible to use secondary light stabilizers of the antioxidant type which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates into the skin. Typical examples are amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocaninic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (eg anserine) , Carotenoids, carotenes (eg α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thioredoxin, glutathione, cysteine, cystine, Cystamine and its glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate , Distearylthiodipropionat, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and Sulfoximinverbindungen (eg Buthioninsulfoximine, Homocysteinsulfoximin, Butioninsulfone, penta-, hexa-, Heptathioninsulfoximin) in very low vert doses (eg pmol to μmol / kg), furthermore (metal) chelators (eg α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (eg citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, Biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate ), Tocopherols and derivatives (eg, vitamin E acetate), vitamin A and derivatives (vitamin A palmitate), and benzylic resin, rutinic acid and their derivatives, α-glycosylrutin, ferulic acid, furfurylidene glucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiacetic acid , Nordihydroguajaretsäure, Trihydroxybutyrophenon, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its D eratives (eg ZnO, ZnSO ₄ ) selenium and its derivatives (eg selenium methionine), stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide) and the derivatives suitable according to the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids) of these drugs.

• Glycerin;
• Alkylenglycole, wie beispielsweise Ethylenglycol, Diethylenglycol, Propylenglycol, Butylenglycol, Hexylenglycol sowie Polyethylenglycole mit einem durchschnittlichen Molekulargewicht von 100 bis 1.000 Dalton;
• technische Oligoglyceringemische mit einem Eigenkondensationsgrad von 1,5 bis 10 wie etwa technische Diglyceringemische mit einem Diglyceringehalt von 40 bis 50 Gew.-%;
• Methyolverbindungen, wie insbesondere Trimethylolethan, Trimethylolpropan, Trimethylolbutan, Pentaerythrit und Dipentaerythrit;
• Niedrigalkylglucoside, insbesondere solche mit 1 bis 8 Kohlenstoffen im Alkylrest, wie beispielsweise Methyl- und Butylglucosid;
• Zuckeralkohole mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Sorbit oder Mannit,
• Zucker mit 5 bis 12 Kohlenstoffatomen, wie beispielsweise Glucose oder Saccharose;
• Aminozucker, wie beispielsweise Glucamin;
• Dialkoholamine, wie Diethanolamin oder 2-Amino-1,3-propandiol.

Hydrotropes, such as, for example, ethanol, isopropyl alcohol, or polyols can also be used to improve the flow behavior. Polyols contemplated herein preferably have from 2 to 15 carbon atoms and at least two hydroxyl groups. The polyols may contain other functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are

• glycerol;
• Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and polyethylene glycols having an average molecular weight of 100 to 1,000 daltons;
• technical oligoglycerine blends having an inherent degree of condensation of from 1.5 to 10 such as technical grade diglycerin blends having a diglycerol content of from 40 to 50 weight percent;
• Methylol compounds, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• Niedrigalkylglucoside, in particular those having 1 to 8 carbons in the alkyl radical, such as methyl and Butylglucosid;
• Sugar alcohols containing 5 to 12 carbon atoms, such as sorbitol or mannitol,
• Sugars having 5 to 12 carbon atoms, such as glucose or sucrose;
• Amino sugars such as glucamine;
• Dialcoholamines, such as diethanolamine or 2-amino-1,3-propanediol.

Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Part A and B of the Cosmetics Regulation. Suitable insect repellents are N, N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535, suitable as a self-tanner is dihydroxyacetone.

As perfume oils are called mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castoreum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, Benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and Methylcedrylketon to the alcohols Anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes and balsams. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Also essential oils of lower volatility, which are mostly used as flavoring components, are suitable as perfume oils, eg sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, a-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linaloof, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, citron oil, Mandarinendl, orange oil, Allylamylglycolat, Cyclovertal, Lavandinöl, Muskateller Sage oil, β-damascone, geranium oil Bourbon, cyclohexyl salicylate, Vertofix Coeur, iso-E-Super, fixolide NP, Evernyl, iraldeine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilllat, lrotyl and Floramat used alone or in mixtures.

As dyes , the substances suitable and suitable for cosmetic purposes can be used, as compiled, for example, in the publication "Cosmetic Colorants" of the Dye Commission of the Deutsche Forschungsgemeinschaft, Verlag Chemie, Weinheim, 1984, pp . 81-106 . These dyes are usually used in concentrations of 0.001 to 0.1 wt .-%, based on the total mixture.

Typical examples of antimicrobial agents are preservatives having specific activity against gram-positive bacteria such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di- (4-chlorophenyl-biguanido) -hexane) or TCC (3,4,4'-trichlorocarbanilide). Also, numerous fragrances and essential oils have antimicrobial properties. Typical examples are the active ingredients eugenol, menthol and thymol in clove, mint and thyme oil. An interesting natural deodorant is the terpene alcohol Famesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in lime blossom oil and has a lily of the valley odor. Glycerol monolaurate has also proven itself as a bacteriostat. The proportion of additional germ-inhibiting agents is usually about 0.1 to 2% by weight, based on the solids content of the preparations.

powder detergents

The detergents and cleaners may contain, in addition to the above-mentioned further typical ingredients such as builders, bleaches, bleach activators, detergency boosters, enzymes, enzyme stabilizers, grayness inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic salts and fragrances and dyes.

As a solid builder in particular fine-crystalline, synthetic and bound water-containing zeolite such as zeolite NaA is used in detergent quality. Also suitable, however, are zeolite NaX and mixtures of NaA and NaX. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22 wt .-% of bound water. Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 is and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European Patent Application EP 0164514 A. Preferred crystalline layered silicates are those in which M in the general formula stands for sodium and x assumes the values 2 or 3. In particular, both β- and γ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, and β-sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171 . The powder detergents according to the invention preferably contain from 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, with mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous. In particular, it is preferred that the agents contain from 20 to 50% by weight of zeolite and / or crystalline layered silicates. Particularly preferred agents contain up to 40% by weight of zeolite and in particular to 35% by weight of zeolite, in each case based on anhydrous active substance. Other suitable ingredients of the compositions are water-soluble amorphous silicates; Preferably, they are used in combination with zeolite and / or crystalline layer silicates. Particular preference is given to agents which contain, above all, sodium silicate with a molar ratio (modulus) of Na ₂ O: SiO _{2 of} from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5. The content of the amorphous sodium silicate compositions is preferably up to 15% by weight and preferably between 2 and 8% by weight. Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates may also be present in small amounts in the compositions. The content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight. In addition, the compositions may additionally contain phyllosilicates of natural and synthetic origin. Such layered silicates are known, for example, from the patent applications DE 2334899 B, EP 0026529 A and DE 3526405 A. Their usability is not on a specific composition or structural formula limited. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates which belong to the group of water-swellable smectites are, for example, those of the general formulas

(OH) ₄ Si _8-y Al _y (Mg _x Al _4-x ) O ₂₀ montmorillonite

(OH) ₄ Si _8-y Al _y (Mg _6-z Li _z ) O ₂₀ hectorite

(OH) ₄ Si _8-y Al _y (Mg _6-z Al _z ) O ₂₀ Saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron may be incorporated in the crystal lattice of the layered silicates according to the above formulas. Furthermore, because of their ion-exchanging properties, the layered silicates may contain hydrogen, alkali, alkaline earth, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or on the type of processing. Useful layered silicates are known, for example, from US Pat. No. 3,966,629, US Pat. No. 4,062,647, EP 0026529 A and EP 0028432 A. Preferably, phyllosilicates are used, which are largely free of calcium ions and strong coloring iron ions due to an alkali treatment. Useful organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures thereof , Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or of polymethacrylic acid, for example those having a molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their molecular weight relative to free acids is generally from 5,000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000. The use of polymeric polycarboxylates is not mandatory. However, if polymeric polycarboxylates are used, agents are preferred which biodegradable polymers, for example terpolymers containing as monomers acrylic acid and maleic acid or salts thereof and vinyl alcohol or vinyl alcohol derivatives or as monomers acrylic acid and 2-alkylallylsulfonic acid or salts thereof and sugar derivatives. In particular, terpolymers are preferred which are obtained according to the teaching of German patent applications DE 4221381 A and DE 4300772 A. Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from Polyolcarbonsäuren such as gluconic acid and / or glucoheptonic acid.

Among the compounds serving as bleaches, which yield hydrogen peroxide in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents are, for example, peroxycarbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25 wt .-%. Preference is given to the use of sodium perborate monohydrate in amounts of from 10 to 20% by weight and in particular from 10 to 15% by weight. Its ability to bind free water to form tetrahydrate contributes to increasing the stability of the agent.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples thereof are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate. The content of the bleach-containing agents in bleach activators is in the usual range, preferably between 1 and 10 wt .-% and in particular between 3 and 8 wt .-%. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Their proportion can be about 0.2 to about 2 wt .-%. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents may contain other enzyme stabilizers. For example, 0.5 to 1 wt .-% sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, it is particularly advantageous to use boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyroboric acid (tetraboric acid H ₂ B ₄ O ₇ ).

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus prevent graying. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, Gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, preference is given to cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof and polyvinylpyrrolidone, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

The agents may contain as optical brighteners derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino group, are a Diethanolamino group, a methylamino group, an anilino group or a 2-Methoxyethylaminogruppe carry. Furthermore, brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used. Uniformly white granules are obtained when the means except the usual brighteners in conventional amounts, for example between 0.1 and 0.5 wt .-%, preferably between 0.1 and 0.3 wt .-%, even small amounts, for example 10 ^-6 to 10 ^-3 wt .-%, preferably by 10 ^-5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product of Ciba-Geigy).

Suitable soil repellents are those which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5,000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups may be about 15 to 100. The polymers are characterized by an average molecular weight of about 5,000 to 200,000 and may have a block, but preferably a random structure. Preferred polymers are those having molar ratios of ethylene terephthalate / polyethylene glycol terephthalate of from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Further preferred are those polymers comprising linking polyethylene glycol units having a molecular weight of 750 to 5,000, preferably from 1000 to about 3000 and a molecular weight of the polymer of about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhöne-Poulenc).

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. For example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

The total amount of auxiliaries and additives may be 1 to 50, preferably 5 to 40 wt .-% - based on the means - amount. The preparation of the agent can be carried out by conventional cold or hot processes; It is preferable to work according to the phase inversion temperature method.

Examples Example 1 (not according to the invention)

Production of a slightly soluble APG-SKET granulate. To 170 kg of a 50% cocoalkyl oligoglucoside paste (Glucopon® 600 CS UP) was added at 50 ° C 37.5 kg of a 40% aqueous solution of Polyacrylatlmethyacrylat (Sokalan CP 5) admixed, the mixture with citric acid to a pH Value of 7 and granulated via a nozzle in a fluidized bed plant for granular drying of Glatt and dried at the same time. There were about 100 kg of a dust-free and non-adhesive granules having a residual water content of 2 wt .-% obtained in a Komgrößenverteilung of 0.2 - 1.6 mm. The product was still free-flowing even under pressure after days. 10 g of this granules dissolved within 5 minutes in 250 ml of water at a temperature of 20 ° C.

Comparative Example 1

200 kg of a 50% Kokosalkyloligoglucosid paste (Glucopon 600 CS UP) were adjusted at 50 ° C with citric acid to a pH of 7 and without the addition of a 40% aqueous solution of Polyacrylatlmethyacrylat (Sokalan CP 5) on a nozzle granulated in a fluidized bed plant for granular drying of the company Glatt and dried at the same time. This gave a sticky granules with a Komgrößenverteilung of 0.5-10 mm and a residual water content of 3 wt.%, Which caked again even at light pressure. 10 g of this granulate took more than 30 minutes in 250 ml of water at a temperature of 20 ° C until they dissolved completely.

Example 2 (not according to the invention)

Production of a readily soluble APG-SKET granulate. To 70 kg of a 50% cocoalkyl oligoglucoside paste (Glucopon 600 CS UP) and 50 kg of a mixture consisting of 35 kg of cocoalkyl oligoglucoside and 15 kg of C 12/14 fatty alcohol, 37.5 kg of a 40% at 50 ° C. aqueous solution of polyacrylate methacrylate (Sokalan CP 5) mixed and granulated via a nozzle in a plant for granular drying of Glatt and dried at the same time. There were about 100 kg of a dust-free and non-sticky granules having a residual water content of 2.5 wt .-% obtained in a particle size distribution of 0.2 to 1.6 mm. The product was still free-flowing even under pressure after days. 10 g of this granules dissolved within 5 minutes in 250 ml of water at a temperature of 20 ° C.

Examples 3 to 18

• (3) Proteinhydroylsat-Pulver (Gluadin WP),
• (4) wasserlösliches Weizengluten,
• (5) Guarhydroxypropyl-trimethylammoniumchlorid (Cosmedia Guar C 261; Fa. Cognis)
• (6) Polyasparaginat (MG 20.000, Fa. Donlar)
• (7) Cyclodextrin
• (8) Dextrin
• (9) Carboxymethyl Dextran
• (10) kationisch modifizierte Cellulose (Polymer JR 400)
• (11) Polyglykol-Polyamin-Kondensationsharz (Polyquart H 81; Fa. Cognis)
• (12) Polyhydroxycarbonsäure, Natrium-Salz-Pulver (Hydagen F; Fa. Cognis)
• (13) VinylpyrrolidonNinylacetat-Copolymer-Pulver (Nasuna B; Fa. Cognis)
• (14) Guarmehl-Pulver (Cosmedia Guar U; Fa. Cognis)
• (15) Chitosan-Pulver (Hydagen HCMF; Fa. Cognis)
• (16) kationisch modifiziertes Proteinhydroylsat (Gluadin WQ; Fa. Cognis),
• (17) Polybeta-Alanine/Glutaric Acid Crosspolymer-Pulvers
• (18) Polyethylglutamat-Pulver
  
  
  
  
  
  

To prepare a readily soluble APG-SKET granulate, the following polymers were used instead of the polyacrylate / methyl acrylate:

• (3) protein hydroylsate powder (Gluadin WP),
• (4) water-soluble wheat gluten,
• (5) guar hydroxypropyl trimethyl ammonium chloride (Cosmedia Guar C 261, Cognis)
• (6) polyasparticin (MW 20,000, Donlar)
• (7) cyclodextrin
• (8) Dextrin
• (9) Carboxymethyl Dextran
• (10) cationically modified cellulose (Polymer JR 400)
• (11) polyglycol-polyamine condensation resin (Polyquart H 81, Cognis)
• (12) Polyhydroxycarboxylic acid, sodium salt powder (Hydagen F, Cognis)
• (13) vinylpyrrolidone-vinyl acetate copolymer powder (Nasuna B, Cognis)
• (14) Guar gum powder (Cosmedia Guar U, Cognis)
• (15) Chitosan powder (Hydagen HCMF, Cognis)
• (16) cationically modified protein hydroxylate (Gluadin WQ, Cognis),
• (17) Polybeta-Alanine / Glutaric Acid Crosspolymer Powder
• (18) Polyethylglutamate powder
  
  
  
  
  
  

Claims (8)

1. Surfactant granulates obtainable by i) dissolving or mixing organic polymeric carrier materials chosen from the group formed by polypeptides, chitin, chitosan, celluloses, polyvinyl alcohols, polyvinylpyrrolidone, polycondensates, polyhydroxycarboxylic acids, polyethylene glycol, polyesters, polyurethanes and/or derivatives thereof in aqueous pastes of nonionic surfactants without addition of anorganic compounds and ii) granulating and simultaneously drying the aqueous mixture of surfactants and organic polymeric carrier materials together.
2. Method for producing surfactant granulates, characterized in that i) organic polymeric carrier materials chosen from the group formed by polypeptides, chitin, chitosan, celluloses, polyvinyl alcohols, polyvinylpyrrolidone, polycondensates, polyhydroxycarboxylic acids, polyethylene glycol, polyesters, polyurethanes and/or derivatives thereof are dissolved or mixed in aqueous pastes of nonionic surfactants without addition of anorganic compounds and ii) the aqueous mixture of surfactants and organic polymeric carrier materials is granulated and simultaneously dried together.
3. Method according to Claim 2, characterized in that nonionic surfactants are used which are chosen from the group formed by alkyl and alkenyl oligoglycosides, fatty acid N-alkylpolyhydroxyalkylamides, alcohol ethoxylates, alkoxylated carboxylic acid esters, and mixtures thereof.
4. Method according to at least one of Claims 2 or 3, characterized in that alkyl and alkenyl oligoglycosides of the formula (I) are used,
   
           R ¹ O-[G] _p      (I)
   
   in which R¹ is an alkyl and/or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is numbers from 1 to 10.
5. Method according to at least one of Claims 2 to 4, characterized in that the surfactant granulates have a particle size distribution between 0.02 and 2.0 mm.
6. Use of surfactant granulates according to Claim 1 in surface-active preparations.
7. Use of surfactant granulates according to Claim 1 in cosmetic and/or pharmaceutical preparations.
8. Use of surfactant granulates according to Claim 1 in detergents and cleaners.