EP1173539A1 - Coated shaped bodies of a detergent and cleansing-agent - Google Patents

Abstract

The invention relates to coated shaped bodies of a detergent and cleansing agent which have advantageous properties, such as a high degree of stability without impairing short disintegration times and a high degree of resistance to impact and abrasive stress. Said shaped bodies are obtained using lower quantities of coating agents, whereby a maximum 1 % by weight, or preferably significantly less of the total shaped body consists of the coating material. Selected water-soluble polymers which can also be mixed with other polymers are suitable for use as the coating materials.

Description

 "Detergent tablets with coating"

The present invention is in the field of compact moldings which have washing and cleaning properties. Such detergent tablets have, for example, detergent tablets for washing textiles, detergent tablets for automatic dishwashing or cleaning hard surfaces. Bleach tablets for use in washing machines or dishwashers, water softening tablets or stain tablets. In particular, the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have towards pulverfb ^'shaped a number of advantages: they are easier to dose and handle and have advantages due to its compact structure during storage and transport. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use. Since sufficiently stable, that is to say molded and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and a consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process. The delayed disintegration of the molded article has the further disadvantage that conventional detergent and molded article articles cannot be washed in via the washing-in chamber of household washing machines, since the tablets do not disintegrate into secondary articles that are small enough to get out in a sufficiently quick time Detergent dispenser to be washed into the washing drum. Another problem that arises in particular with detergent tablets is the friability of the tablets or their often insufficient stability against abrasion. Sufficiently break-resistant, ie hard, detergent molded articles can be produced, but these are often not able to withstand the stresses associated with packaging, transport and handling, ie falling and rubbing loads, so that edge breakage and abrasion phenomena impair or impair the appearance of the molded article even lead to a complete destruction of the molded body structure.

To overcome the dichotomy between hardness, i.e. Transport and handling stability, and easy disintegration of the molded body, many approaches have been developed in the prior art. A particularly well-known approach from pharmacy and extended to the field of detergent tablets is the incorporation of certain disintegration aids which facilitate the access of water or which swell or develop gas or other forms upon access of water. Other proposed solutions from the patent literature describe the cessation of premixes of certain particle sizes, the separation of individual ingredients from certain other ingredients and the coating of individual ingredients or the entire molded article with binders.

The coating of detergent tablets, which is also increasingly referred to as "coating" in German, is the subject of several patent applications.

The European patent applications EP 846 754, EP 846 755 and EP 846 756 (Procter & Gamble) describe coated detergent tablets which comprise a "core" of compressed, particulate detergents and cleaning agents and a "coating", the coating materials being dicarboxylic acids, in particular Adipic acid may be used, which may contain other ingredients such as disintegration aids. Coated detergent tablets are also the subject of European patent application EP 716 144 (Unilever). According to the information in this document, the hardness of the tablets can be increased by "coating" without impairing the disintegration and dissolving times. Film-forming substances, in particular copolymers of acrylic acid and maleic acid or sugar, are mentioned as coating agents.

Only little information about the application of the coating can be found in all the documents mentioned. Information on the thickness of the coating layer is also missing.

While according to the teaching of the first-mentioned documents, well over 5% by weight of the total weight of the coated tablet consist of coating material, according to the teaching of the latter-mentioned document, it is still at least 1% by weight. In addition, the approaches from the prior art also require individual packaging of the molded bodies. Here, the molded body as a single molded body or as a dosing unit, which may consist of two molded bodies, for example, must be packed in foil so that the tablets lose neither their high hardness nor their rapid disintegration properties during storage. Only after this repackaging of individual molded bodies can the entire package that is delivered to the retailer be packed.

The present invention was based on the object of providing coated detergent and shaped articles in which the advantageous properties of the higher hardness are achieved without impairing the short disintegration times with smaller amounts of coating agents, with a maximum of 1% by weight, preferably significantly less, of the total Molded bodies should be made out of the coating material. In particular, the resistance of the molded bodies to falling and friction loads compared to the known molded bodies should be further improved despite the significantly reduced use of coating materials. In the ideal case, the coated molded articles should be able to be delivered to the retailer with minimized packaging expenditure, ie with a more cost-effective individual packaging or even without any individual packaging, without the storage stability of the molded articles suffering as a result. An easy to carry out and universally applicable manufacturing process To provide such coated molded body was a further object of the present invention.

It has now been found that certain water-soluble polymers, even in extremely small amounts, are suitable for coating detergent tablets and impart advantageous properties to them.

The invention therefore relates to detergent tablets made of compressed particulate detergent and detergent, containing builders (e), surfactant (s) and, if appropriate, further detergent and detergent components which are coated with a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture is selected from

a) water-soluble nonionic polymers from the group of

al) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the group of

b 1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of

c 1) Acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) Acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

dl) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide teφolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid

Methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinked d6) by copolymerization at least one monomer from each of the following three

Copolymers obtained in groups: d6i) esters of unsaturated alcohols and short-chain saturated

Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, dόii) unsaturated carboxylic acids, dόiii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group dόii) with saturated or unsaturated, straight-chain or branched C ₈ _ι ₈ -

Alcohol d7) Teφolymers of crotonic acid, vinyl acetate and an allyl or

Methallyl esters d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters of ethylene with one or more copolymers of crotonic acid , Vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts dlO) Teφolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic branched in the α-position monocarboxylic acid

e) water-soluble cationic polymers from the group of

el) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammomium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate6) Vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) under the INCI names Polyquatemium 2, Polyquatemium 17,

Polyquatemium 18 and Polyquatemium 27 indicated polymers. Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.

The detergent tablets according to the invention are coated with a polymer or polymer mixture, the polymer (and accordingly the entire coating) or at least 50% by weight of the polymer mixture (and thus at least 50% of the coating) being selected from certain polymers. The coating consists entirely or at least 50% of its weight of water-soluble polymers from the non-ionic, amphoteric, zwitterionic, anionic and / or cationic polymers. These polymers are described in more detail below.

Water-soluble polymers preferred according to the invention are nonionic. Suitable nonionic polymers are, for example:

Polyvinylpyrrolidones, such as those sold under the name Luviskol (BASF). Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention.

Polyvinylpyrrolidones [poly (l-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750,000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinyl pyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

VinylpyrrolidonyNinylester copolymers, such as those sold under the trademark LuviskoL (BASF). Luviskol * ^' VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.

The vinyl ester polymers are polymers accessible from vinyl esters with the grouping of the formula (II)

_ CH ₂ - CH - o

as a characteristic basic building block of macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates are by far the most important technical representatives.

The vinyl esters are polymerized by free radicals using various processes (solution polymerization, suspension polymerization,

Emulsion polymerization, bulk polymerization.). Copolymers of vinyl acetate with vinyl pyrrolidone contain monomer units of the formulas (I) and (II)

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methylhydroxypropyl cellulose, as sold for example under the trademark Culminal® ^® and Benecel ^® (AQUALOΝ). Cellulose ethers can be described by the general formula (III)

in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish white, odorless and tasteless powders in widely differing degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers include amphoteric polymers, ie polymers that contain free amino groups as well as free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - COO ^" - or -SO ^~ groups, and summarized such polymers that contain -COOH or SO H groups and quaternary ammonium groups. An example of an amphopolymer usable according to the invention is the acrylic resin available under the name Amphomer ^® , the is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, methacrylic acid and their simple esters. Also preferred amphopolymers are composed of unsaturated carboxylic acids (eg acrylic - and methacrylic acid), cationically derivatized unsaturated carboxylic acids (eg acrylamidopropyl-trimethyl-ammonium chloride) and g if necessary other ionic or nonionic monomers together, as can be seen, for example, in German Offenlegungsschrift 39 29 973 and the prior art cited therein. Tepolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat ^® 2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are, for example, the Octylacryl- available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) amide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-Hydroxypropylmethacrylat- copolymers.

Suitable zwitterionic polymers are, for example, the polymers disclosed in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are available under the name Amersette® ^® (AMERCHOL).

Anionic polymers suitable according to the invention include a .:

Vinyl acetate / crotonic acid copolymers, such as are commercially available for example under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF).

In addition to monomer units of the aforementioned formula (II), these polymers also have monomer units of the general formula (IV):

[-CH (CH ₃ ) -CH (COOH) -] _n (IV)

Vinyl pyrrolidone vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF). A preferred polymer is that available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymers. Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide particles, which are sold, for example, under the name Ultrahold ^® strong (BASF).

Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or

Methacrylic acid alone or as a mixture with other copolymerisable

Compounds on polyalkylene glycols are obtained by hot polymerization in a homogeneous phase in that the polyalkylene glycols in the

Monomers of vinyl esters, esters of acrylic acid or methacrylic acid, are stirred in the presence of radical formers.

Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate,

Vinyl butyrate, vinyl benzoate and, as esters of acrylic acid or methacrylic acid, those which are associated with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-

Propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-l-

Propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-l-

Butanol, 1-hexanol, are available, proven.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula V

H- (O-CH ₂ -CH ₂ ) _n -OH (V)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc). Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula VI

H- (O-CH-CH,) _n -OH (VI)

I.

CH _{3 is} sufficient, where n can have values between 1 (propylene glycol) and several thousand. Technically important are di-, tri- and

Tetrapropylene glycol, i.e. the representatives with n = 2, 3 and 4 in formula VI.

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and

Crotonic acid can be used. grafted and crosslinked copolymers from the copolymerization of i) at least one monomer of the non-ionic type, ii) at least one monomer of the ionic type, iii) of polyethylene glycol and iv) a crosslinker

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000. The non-ionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-witch. The non-ionic monomers can likewise be of very different types, of which crotonic acid, allyloxyacetic acid, Vinyl acetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the graft polymers.

Preferred crosslinkers are ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule of saccharin.

The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight - at least one monomer of the nonionic type, ii) 3 to 80% by weight of at least one monomer of the ionic type, iii) 2 to 50% by weight, preferably 5 to 30% by weight, of polyethylene glycol and iv) 0.1 to 8% by weight of a crosslinker, the percentage of the crosslinker being determined by the ratio of the total weights of i), ii) and iii ) is trained. Copolymers obtained by copolymerizing at least one monomer from each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated

Carboxylic acids, ii) unsaturated carboxylic acids, iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C ₈ -C ₈ alcohols. Short-chain carboxylic acids or alcohols include those with To understand 1 to 8 carbon atoms, where the carbon chains of these compounds may optionally be interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.

Teφolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester These teφolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula VII:

(VII)

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched Cι- ₆ alkyl radical and the sum of

Carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

The above-mentioned polymers preferably result from the

Copolymerization of 7 to 12 wt .-% crotonic acid, 65 to 86 wt .-%, preferably 71 to 83 wt .-% vinyl acetate and 8 to 20 wt .-%, preferably 10 to 17 wt .-% allyl or methallyl esters of formula VII.

Tetra- and penta-polymers of i) crotonic acid or allyloxyacetic acid ii) vinyl acetate or vinyl propionate iii) branched allyl or methallyl esters iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters

Crotonic acid copolymers with one or more monomers from the group

Ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts

Teφolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position.

Other polymers which can preferably be used as part of the coating are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, polymers which have a cationic group irrespective of the pH of the agent (ie both the coating and the molded body) are referred to as “permanently cationic”. These are generally polymers which have a quaternary nitrogen atom, for example in the form of a Preferred cationic polymers are, for example, quaternized cellulose derivatives, as are commercially available under the names Celquat ^® and Polymer JR ^® The compounds Celquat ^® H 100, Celquat ^® L 200 and Polymer JR ^® 400 are preferred quaternized cellulose . derivatives, polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicon), Dow Coming ^® 929 emulsion (containing a hydroxylamino- modified silicone, which is also called amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) as well as Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxane, Quaternium -80),

Cationic guar derivatives, such as in particular the products marketed under the trade names Cosmedia ^® Guar and Jaguar ^® ,

Polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (Dimefhyl- diallyl ammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.

Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as, for example, vinyl pyrrolidone-dimethylaminomethacrylate copolymers quaternized with diethyl sulfate. Such compounds are commercially available under the names Gafquat ^® 734 and Gafquat ^® 755. Vinylpyrrolidone methoimidazolinium chloride copolymers such as those sold under the name Luviquat ^®, quaternized polyvinyl alcohol, as well as those known under the designations Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 polymers having quaternary nitrogen atoms in the polymer main chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, to which express reference is made here becomes.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic Cellulose derivatives, in particular the commercial product Polymer ^® JR 400, are very particularly preferred cationic polymers.

The shaped detergent tablets according to the invention already have significantly improved properties even with small amounts of coating material. It is preferred in the context of the present invention that the amount of coating material makes up less than 1% by weight, preferably less than 0.5% by weight and in particular less than 0.25% by weight of the total weight of the coated molded article . Detergent molded articles in which the weight ratio of uncoated molded article to coating is greater than 100 to 1, preferably greater than 250 to 1 and in particular greater than 500 to 1, are therefore preferred embodiments of the present invention.

The small amounts in which the abovementioned polymers already result in a highly resilient and advantageous coating of the previously molded detergent and cleaning product bodies make it possible to achieve coating thicknesses which are small in comparison to the dimensions of the molding bodies. In preferred detergent tablets, the thickness of the coating on the tablet is 0.1 to 150 μm, preferably 0.5 to 100 μm and in particular 5 to 50 μm.

In order to make the coating even more resistant to mechanical stress, polyurethanes can be incorporated into the coating. These impart elasticity and stability to the coating and can make up to 50% by weight of the coating after the amount of water-soluble polymer indicated above.

For the purposes of the invention, polyurethanes are water-insoluble if they are less than 2.5% by weight> soluble in water at room temperature.

The polyurethanes consist of at least two different types of monomers, a compound (A) with at least 2 active hydrogen atoms per molecule and a di- or polyisocyanate (B). The compounds (A) can be, for example, diols, triols, diamines, triamines, polyetherols and polyesterols. The compounds with more than 2 active hydrogen atoms are usually used only in small amounts in combination with a large excess of compounds with 2 active hydrogen atoms.

Examples of compounds (A) are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, di-, tri-, tetra- and poly-ethylene and propylene glycols, copolymers of lower alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, Ethylene diamine, propylene diamine, 1,4-diaminobutane, hexamethylene diamine and α, ω-diamines based on long-chain alkanes or polyalkylene oxides.

Polyurethanes in which the compounds (A) are diols, triols and polyetherols can be preferred according to the invention. In particular, polyethylene glycols and polypropylene glycols with molecular weights between 200 and 3000, in particular between 1600 and 2500, have proven to be particularly suitable in individual cases. Polyesterols are usually obtained by modifying compound (A) with dicarboxylic acids such as phthalic acid, isophthalic acid and adipic acid.

The compounds (B) used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluene diisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular

Isophorone diisocyanate used. These compounds can be described by the general formula VIII:

O = C = N-R -N = C = O (VIII),

in which R ^{4 stands} for a connecting grouping of carbon atoms, for example a methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. group. In the above-mentioned, most widely used hexamethylene diisocyanate (HMDI), R ⁴ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluenediisocyanate (TDI) R ⁴ stands for C ₆ H ₃ - CH ₃ ) , in 4,4'-methylenedi (phenyl isocyanate) (MDI) for C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) and in isophorone diisocyanate R ^{4 represents} the isophorone residue (3,5,5-trimethyl-2-cyclohexenone) . Furthermore, the polyurethanes used according to the invention can also contain building blocks such as diamines as chain extenders and hydroxycarboxylic acids. Dialkylolcarboxylic acids such as dimethylolpropionic acid are particularly suitable hydroxycarboxylic acids. With regard to the other building blocks, there is no fundamental restriction as to whether the building blocks are nonionic, anionic or cationic.

With regard to further information on the structure and manufacture of the polyurethanes, reference is expressly made to the articles in the relevant reference works such as Römpps Chemical Lexicon and Ullmanns Encyclopedia of Industrial Chemistry.

Polyurethanes, which can be characterized as follows, have proven particularly suitable according to the invention in many cases:

- only aliphatic groups in the molecule

- No free isocyanate groups in the molecule

- Polyether and Polyesteφolyurethane

- anionic groups in the molecule.

Furthermore, it has proven to be advantageous for the production of the coated detergent tablets according to the invention if the polyurethanes are not mixed directly with the other components, but instead are introduced in the form of aqueous dispersions. Such dispersions usually have a solids content of approximately 20-50%, in particular approximately 35-45%, and are also commercially available.

Detergent tablets, in which the coating, in addition to the polymers mentioned, is based on polyurethanes in quantities of 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 30% by weight on the coating, are preferred according to the invention. The components of the coating of the moldings according to the invention have been described in more detail above. The components of the molded body itself, ie the uncoated molded body, are described below. These shaped bodies are referred to below in part as “basic shaped bodies” in order to achieve a verbal delimitation against the term “shaped body” or “tablet” for the detergent shaped body coated according to the invention, but in some cases the general term “shaped body” is also used. Since the subject matter of the present invention is provided with a basic molded article, the information given below for the basic molded article naturally also applies to detergent molded articles according to the invention which meet the corresponding conditions, and vice versa.

The basic molded articles contain as essential components builders (e) and surfactants (e). The basic moldings according to the invention can contain all builders customarily used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Suitable crystalline schichtf ^'-shaped sodium silicates have the general formula NaMSi _x θ ₂ + χ ^ι' H ₂ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred Values for x are 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 θ ₅ ^' VH 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 .

Amorphous sodium silicates with a module Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can be done in different ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". 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 are added

Electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be integrated in such a way 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 silicates, which also have a delay in dissolving compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X) , which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O ^• (ln) K ₂ O ^• Al ₂ O ₃ ^' (2 - 2.5) SiO ₂ ' (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular compound, and can also be used for a kind of "powdering" of the entire mixture to be vesφress, usually both ways of incoφoration of the zeolite in the premix. Suitable zeolites have an average particle size of less than 10 microns (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO) _n and orthophosphoric acid H PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or calcareous stations in fabrics and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^" , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O) and Maddrell's salt (see below). NaH ₂ PO is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like ^"3 , water loss at 95 °), 7 mol. (Density 1.68 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1.52 like ^"3 , melting point 35 ° with the loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes into the diphosphate Na P ₂ θ ₇ upon heating. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with sodium carbonate solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or Dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO, are colorless crystals, which like dodecahydrate have a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39 ^ 40% P ₂ O ₅ ) a density of 2.536 gcm ^"J. Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or three-base potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^" , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It occurs, for example, when heated of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na P ₂ θ ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), KP ₂ O _7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^"-3, which is soluble in water, wherein the pH value of l% solution at 25 ° is 10.4. Condensation of the NaH ₂ PO or the KH PO produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ Oιo (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O - Well with n = 3. Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ Oιo (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) on the market. The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of Sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates can be used in the basic shaped bodies. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which 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), as long as 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. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

Polymeric polycarboxylates are also suitable as builders, for example the 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 _{s 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 due to its structural relationship with the investigated polymers provides realistic molecular weight values. 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 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

Also suitable are copolymeric polycarboxylates, 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 relative molecular weight, based on free acids, is generally 2,000 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 used either as a powder or as an aqueous solution. The content 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 contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers . Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that in addition to cobuilder properties they also have a bleach-stabilizing effect.

Other 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. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose sirape with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

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 US Pat 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 are known. 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, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 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 contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the compositions also contain bleach, it may be preferred to use aminoalkanephosphonates, in particular to use DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

The amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. The amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight) , for example detergent tablets (usually 10 to 50 wt .-%>, preferably 12.5 to 45 wt .-% and in particular between 17.5 and 37.5 wt .-% ι).

Preferred basic molded articles furthermore contain one or more surfactant (s). Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the basic shaped body. Mixtures of anionic and nonionic surfactants are preferred from an application point of view. The total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C. ₁₃ - Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained, for example, from Ci ₂ -ι ₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonate starting products , into consideration. Also suitable are alkanesulfonates, the -ι from C ₂ alkanes are obtained for example by Sulfochlorierang or sulfoxidation and subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfated products of saturated fatty acids having 6 to 22 carbon atoms, for example capric acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C10-C20 oxo alcohols and those Half-secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ - Ci ₆ alkyl sulfates and C ₂ -Ci ₅ alkyl sulfates and C ₄ -C ₅ alkyl sulfates are preferred for reasons of washing technology. In addition, 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _{7-2 ]} alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl-branched C ₉ _n alcohols with an average of 3.5 mol ethylene oxide (EO) or C ₂ - _{. 8} fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight. Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _{8-0 8} fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated eraacic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or taig fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having 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 may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. ₁₄ - - The preferred ethoxylated alcohols include, for example, ₁₂ C, alcohols containing 3 EO or 4 EO, C ₉ n-alcohol with 7 EO, C, _{3, 5} alcohols containing 3 EO, 5 EO, 7 EO or 8 EO. , Cι _2. ] ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci ₂ -ι ₄ alcohol with 3 EO and Cι ₂ -ι ₈ alcohol with 5 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 this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 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.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (IX), R ^]

R-CO-N- [Z] (IX)

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R * 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. The polyhydroxy fatty acid amides are known substances which can usually be obtained 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 ester or a fatty acid chloride.

The grappa of polyhydroxy fatty acid amides also include compounds of the formula (X)

R ^] -OR ²

R-CO-N- [Z] (X) in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, preference being given to C ₄ -alkyl or phenyl radicals and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which has at least two Hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably obtained by reductive amine rank of a reduced sugar, for example glucose, fractose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of international application WO-A-95/07331, by reaction with Fatty acid methyl esters can be converted into the desired polyhydroxy fatty acid amides in the presence of an alkoxide as catalyst.

In the context of the present invention, basic shaped bodies are preferred which contain anionic (s) and nonionic (s) surfactant (s), application-specific advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used.

For example, base moldings are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2 is. Also preferred are detergent tablets which contain anionic and / or nonionic surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5% by weight and in particular above of 10% by weight, based in each case on the molded body weight. Particularly preferred are detergent tablets, the surfactant (s), preferably anionic (s) and / or nonionic (s) surfactant (s), in amounts of 5 to 40% by weight, preferably 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt.%, each based on the molded body weight.

From an application point of view, it can be advantageous if certain classes of surfactant in some phases of the basic molded article or in the entire molded article, i.e. in all phases, are not included. A further important embodiment of the present invention therefore provides that at least one phase of the molded article is free from nonionic surfactants.

Conversely, a positive effect can also be achieved by the content of individual phases or the entire molded article, ie all phases, of certain surfactants. The introduction of the alkyl polyglycosides described above has proven to be advantageous, so that basic molded bodies are preferred in which at least one phase of the molded body contains alkyl polyglycosides. Similar to nonionic surfactants, the omission of anionic surfactants from individual or all phases can result in basic form bodies which are more suitable for certain areas of application. It is therefore also conceivable within the scope of the present invention for detergent tablets to be made in which at least one phase of the tablet is free from anionic surfactants.

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times. According to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology ^' " (6th edition, 1987, p. 182-184), tablet disintegrants or disintegrants are understood as auxiliary substances which are suitable for the rapid Disintegration of tablets in water or gastric juice and release of the pharmaceuticals in an absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred basic form tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the molded article.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred basic shaped bodies such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. and in particular contain 4 to 6% by weight. Pure cellulose has the formal bratto composition (C ₆ HιoO ₅ ) _n and formally considered a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets, which contain disintegrants in granular or, optionally, granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The coarser ones mentioned above and described in more detail in the cited documents Disintegration aids based on cellulose are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel * 'TF-30-HG from Rettenmaier.

Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%>) undamaged. A subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

Detergent tablets preferred in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. % and in particular from 4 to 6% by weight, in each case based on the molded body weight, preferred disintegration aids having average particle sizes above 300 μm, preferably above 400 μm and in particular above 500 μm.

In addition to the constituents mentioned, builders, surfactants and disintegration auxiliaries, the detergent tablets according to the invention can contain further ingredients customary in detergents and cleaners from the category of bleaches, bleach activators, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, Color transfer inhibitors and corrosion inhibitors included.

In order to develop the desired bleaching performance, the detergent tablets of the present invention can contain bleaches. Here the common bleaches from the Grappe sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate have proven particularly useful.

“Sodium percarbonate” is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ 3 H2O2 and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^"3 , which easily disintegrates into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by ethanol precipitation from a solution of sodium carbonate in hydrogen peroxide, but was mistakenly regarded as peroxy carbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide plant compound, but the historical name "sodium percarbonate" has become established in practice.

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight> mother liquor, is then centrifuged off and dried in fluidized bed dryers at 90.degree. The bulk density of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and materials used for coating are widely described in the patent literature. In principle, according to the invention, all commercially available types of percarbonate can be used, such as those offered by Solvay Interox, Degussa, Kemira or Akzo. In the bleaching agents used, the content of these substances in the shaped bodies depends on the intended use of the shaped bodies. While conventional universal detergents in tablet form contain between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight of bleaching agent, the contents of bleaching agent or bleach booster tablets are between 15 and 50% by weight, preferably between 22.5 and 45% by weight or in particular between 30 and 40% by weight.

In addition to the bleaching agents used, the detergent tablets according to the invention can contain bleach activator (s), which is preferred in the context of the present invention. Bleach activators are incorporated into detergents and cleaning agents to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetoxy and 2,5-diacetyloxy and 2,5-glycethylacetyl, ethylene glycol 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu Complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

If the molded articles according to the invention contain bleach activators, they each contain, based on the total molded article, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight, of one or more Bleach activators or bleach catalysts. These quantities can vary depending on the intended use of the molded articles produced. For example, bleach activator contents of between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight, are common in typical universal detergent tablets, while bleach tablets contain quite high contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight. and in particular can have between 10 and 20% by weight. The person skilled in the art is not restricted in his freedom of formulation and can thus produce more or less bleaching detergent tablets, detergent tablets or bleach tablets by varying the bleach activator and bleach content.

A particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred shaped detergents and cleaning agents are characterized in that tetraacetylethylenediamine is used as the bleach activator in the amounts mentioned above.

In addition to the constituents mentioned, bleaching agent, bleach activator, builder, surfactant and disintegration aid, the detergent tablets according to the invention can contain further ingredients common in detergents and cleaning agents from the grape dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, Color transfer inhibitors and corrosion inhibitors included. In order to improve the aesthetic impression of the detergent tablets according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

Preferred for use in the detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue tones. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. For example, anionic colorants, for example anionic nitroso dyes, are suitable. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020). Which as a commercial product ^® for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes. Other colorants include Pigmosol ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan ^® Rhodamine EB400 (CI 45100), Basacid ^® Yellow 094 (CI 47005), Sicovit ^® Patentblau 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol ^® Blau GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan ^® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the oxidation sensitivity, the concentration of the colorant in the washing or cleaning agents varies. In the case of colorants which are readily water-soluble, for example the one mentioned above Basacid * green or the above-mentioned Sandolan ^* blue, colorant concentrations are typically chosen in the range from a few 10 ^"2 to 10 ^{" 3} % by weight. In contrast, in the case of the pigment dyes which are particularly preferred on the basis of their brilliance, but less readily water-soluble, for example the above-mentioned Pigmosol "dyes, the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 ^" to 10 ^" % by weight.

The moldings can contain optical brighteners of the type of derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, which instead of the Moφholino Grappe a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyτyl) - diphenyls. Mixtures of the aforementioned brighteners can also be used. The optical brighteners are in the detergent tablets according to the invention in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight. %, each based on the entire molded body, used.

Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially "typical and distinctive" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpionate, allyl cyclohexyl propyl pionate. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, for example the jonones, isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linaloolol and phenylethylol phenolethylol , The hydrocarbons mainly include the teφene such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citras, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content of the detergent tablets according to the invention is usually up to 2% by weight of the total formulation. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and their genetically modified variants are particularly suitable enzymatic agents. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.

In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

The molded body according to the invention are produced in two steps. In the first step, detergent tablets are produced in a manner known per se by squeezing particulate detergent and cleaning agent compositions, and the second step is provided with the coating.

Another object of the present invention is therefore a process for the production of coated laundry detergent and cleaning product bodies by known compression of a particulate washing and

Detergent composition and subsequent immersion in or spraying with a melt, solution or dispersion of one or more polymers from the Grappe

a) water-soluble nonionic polymers from the Grappe of

al) polyvinylpyrrolidones, a2) vinylpyrrolidone-vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the Grappe

b 1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid -

Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the Grappe

cl) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers

d) water-soluble anionic polymers from the Grappe group

dl) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide tepolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid

Methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) by copolymerization at least one monomer from each of the following three

Copolymers obtained in groups: d6i) esters of unsaturated alcohols and short-chain saturated

Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, dόiii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of Grappe dόii) with saturated or unsaturated, straight-chain or branched C ₈ _ι ₈ -

Alcohol d7) Teφolymers of crotonic acid, vinyl acetate and an allyl or

Methallyl esters d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters with one or more copolymers of d9) crotonic acid

Group ethylene, vinylbenzene, vinylmethylether, acrylamide and their water-soluble salts dlO) Teφolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the Grappe

el) quaternized cellulose derivatives e2) polysiloxanes with quaternary groups e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate6) Vinyl pyrolidone-methoimidazolinium chloride copolymers e7) Quaternized polyvinyl alcohol e8) Polymers given the INCI names Polyquatemium 2, Polyquatemium 17, Polyquatemium 18 and Polyquatemium 27.

Analogous to the statements regarding the detergent tablets according to the invention, the polymers mentioned are also preferred in the process according to the invention, so that reference can be made to the statements above.

A description of the two major process steps follows.

The molded articles to be coated later according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular compresses to tablets, using conventional methods. To produce the molded body, the premix is compressed in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix. As the tableting continues, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and an even higher pressure occurs Sintering the premix. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper punch used to build up the drain, the lower punch also moves towards the upper punch during the pressing process, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower stamp, but several stamps can also be attached to one eccentric disc, the number of die holes being correspondingly increased. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower punch, whereby the press-back can in turn be built up only by the upper or lower punch, but also by both stamps. The die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation. At those points where a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are followed additional low-pressure pieces, low-tension rails and lifting tracks supported. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a container for the premix. The pressure on the pre-mix can be individually adjusted via the pressure paths for the upper and lower punches, with the build-up of the pressure occurring when the punch shaft heads roll past adjustable pressure rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. Using suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million molded articles per hour.

When tableting with concentricity presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations in weight can be achieved in the following ways:

- Use of plastic inserts with small thickness tolerances

- Low number of revolutions of the rotor

- Big filling shoes

- Matching the filler paddle speed to the speed of the rotor

- Filling shoe with constant powder height

- Decoupling of filling shoe and powder feed All non-stick coatings known from the art are suitable for reducing stamp caking. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible. In the case of rotating stamps, a plastic insert can generally be dispensed with. The stamp surfaces should be electropolished here.

It was also shown that long pressing times are advantageous. These can be set with drack rails, several drack rollers or low rotor speeds. Since the fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces, systems should be used which limit the pressing force. Here elastic stamps, pneumatic compensators or resilient elements can be used in the force path. The pressure roller can also be designed to be resilient.

Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hom & Noack Pharmatechnik GmbH, Worms, LMA Veφackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liveφool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ). For example, the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkzeuge are for example from the companies Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hom & Noack, Pharmatechnik GmbH, Worms, Ritter Pharmatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all sensibly manageable come as spatial form Configurations into consideration, for example the design as a table, the rod or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. However, it is also possible to form compacts which combine a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined breaking points. For the use of textile detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from approximately 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.

The spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process. However, it is of course also possible to use the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.

Another preferred molded body that can be manufactured has a plate-like or panel-like structure with alternately thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, are broken off and into the Machine can be entered. This principle of the "bar-shaped" shaped body detergent can also be used in others geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides, are realized.

However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in one of the inner layers, while in the case of the stacked molded body the two outer layers and in the case of the shell-shaped molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like. In addition to the layer structure, multi-phase molded bodies can also be produced in the form of toroidal core tablets, core-coated tablets or so-called “bulleye” tablets. An overview of such embodiments of multi-phase tablets is described in EP 055 100 (Jeyes Group). This document discloses toilet block detergents which are shaped Bodies made from a slowly dissolving detergent composition, in which a bleach tablet is embedded.This document simultaneously discloses the most varied configurations of multi-phase molded bodies, from simple multi-phase tablets to complicated multilayer systems with inlays.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined by means of the measured quantity of the diametrical field response. This can be determined according to

2P σ = ^■ πDt

Herein σ stands for diametrical fracture stress (DFS) in Pa, P is the force in N, which leads to the pressure exerted on the molded body, which causes the broke of the molded body, D is the molded body diameter in meters and t the height of the molded body.

Preferred manufacturing processes for detergent tablets are based on a surfactant-containing granulate which is processed with further processing components to form a particulate premix to be treated. Completely analogous to the above statements about preferred ingredients of the detergent tablets according to the invention, the use of further ingredients can also be transferred to their production. In preferred processes, the particulate premix additionally contains granulate (s) containing surfactant and has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g 1. In preferred methods according to the invention, the surfactant-containing granulate has particle sizes between 100 and 2000 μm, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

The further ingredients of the detergent tablets according to the invention can also be incorporated into the method according to the invention, for which reference is made to the above statements. Preferred processes are characterized in that the particulate premix additionally contains one or more substances from the category of bleaching agents, bleach activators, disintegration aids, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Contains color transfer inhibitors and corrosion inhibitors.

The second step of the method according to the invention comprises the application of the coating. For this purpose, common methods of coating bodies can be used, in particular immersing the body in or spraying the body with a melt, solution or dispersion of the polymers mentioned.

Since the immersion of detergent tablets in melts or solutions or dispersions leads to the desired thin coatings only with great technical effort, it is preferred in the context of the present invention to spray polymer solutions or dispersions onto the tablets, the solution or Dispersant evaporates and leaves a coating on the molded body. In preferred processes according to the invention, an aqueous solution of one or more polymers from groups a) to e) is sprayed onto the molded body, the aqueous solution, based in each case on the solution, 1 to 20% by weight, preferably 2 to 15% by weight .-%> and in particular 4 to 10 wt .-% polymer (s) from groups a) to e), optionally up to 20 wt .-% o, preferably up to 10 wt .-% and in particular below 5 % By weight of one or more water-miscible solvents and the balance water.

In order to shorten the drying time, further water-miscible volatile solvents can be added to the aqueous solution. These originate in particular from the alcohol category, ethanol, n-propanol and iso-propanol being preferred. For cost reasons, ethanol and isopropanol are particularly recommended.

The polymers from grappa a) to e) make up 50 to 100% by weight of the coating of the shaped bodies according to the invention. Accordingly, the solution to be sprayed onto the molded body may contain further ingredients, with an addition of polyurethanes - as mentioned above - being preferred. If water-insoluble polyurethanes are added, the liquid to be sprayed on is in the form of a dispersion.

A further preferred embodiment of the process according to the invention is therefore a process variant in which an aqueous dispersion of one or more polyurethanes, which additionally contains one or more dissolved polymers from groups a) to e), is sprayed onto the moldings, the dispersion, in each case based on the dispersion, 1 to 20% by weight, preferably 2 to 15% by weight> and in particular 4 to 10% by weight> polyurethane (s), 1 to 20% by weight, preferably 2 to 15% by weight .-%> and in particular 4 to 10 wt .-%> polymer (s) from groups a) to e), optionally up to 20 wt .-%>, preferably up to 10 wt .-% and in particular below 5 wt .-% of one or more water-miscible solvents and the rest water.

Aqueous dispersions within the meaning of the invention are understood to mean those dispersions whose outer phase consists predominantly of water. The outer phase can also contain other water-miscible solvents such as ethanol and iso-propanol; these further solvents are contained in a maximum of up to 20% by weight, based on the total composition. The outer phase preferably contains water as the sole solvent; a further preferred embodiment contains in the outer phase, based on the total agent, no more than 5% of further solvents. Such aqueous solutions or dispersions can be sprayed on in different ways which are familiar to the person skilled in the art. For example, the solution or dispersion can be fed to a nozzle by means of a pump system, where the solution or dispersion is atomized finely by the high shear forces. The resulting spray mist can then be directed onto the shaped bodies to be coated, which are subsequently optionally dried with the aid of suitable measures (for example blowing with heated air). However, it is also possible to use a multi-component nozzle and to atomize the aqueous solutions or dispersions with the aid of a gas stream through the nozzle. In the simplest case, a two-substance nozzle is used and compressed air is used as the carrier gas. In order to protect the dispersion from oxidation or other interactions with the carrier gas, if necessary, other carrier gases such as nitrogen, noble gases, lower alkanes or ethers can also be used.

It is also possible to reduce the water content of the dispersion or solution, which shortens drying times, minimizes interactions with moisture-sensitive ingredients on the surface of the molded body and lowers production costs. Here, too, the above-mentioned lower alcohols are suitable as solvents, with completely water-free solvent mixtures being less preferred, since certain amounts of water favor the formation of a uniform coating layer. In preferred processes according to the invention, a solution or dispersion of one or more polymers from groups a) to e) in a solvent or solvent mixture from the group of water, ethanol, propanol, iso-propanol, n-heptane and mixtures thereof with the aid of inert Propellants from the group nitrogen, nitrous oxide, propane, butane, dimethyl ether and mixtures thereof are sprayed onto the molded body.

In such preferred process variants according to the invention, the solutions or dispersions advantageously have the following composition, the details relating in each case to the dispersion to be sprayed on: i) 30 to 99% by weight, preferably 40 to 90% by weight and in particular 50 to 85

% By weight of ethanol, propanol, isopropanol, n-heptane or mixtures thereof, ii) 0 to 20, preferably 1 to 15 and in particular 2 to 10% by weight> water, iii) 1 to 50, preferably 2 to 25 and in particular 3 to 10% by weight of one or more polymers from grappa a) to e).

If polyurethanes or other ingredients are to be part of the coating, these can be the polymers from groups a) to e) in the abovementioned. Replace frame recipe up to 50% of the stated weight.

Other ingredients of the dispersions to be sprayed on can be, for example, colorants or fragrances or pigments. Such additives improve, for example, the visual or olfactory impression of the molded bodies coated according to the invention. Dyes and fragrances have been described in detail above. Examples of suitable pigments are white pigments such as titanium dioxide or zinc sulfide, pearlescent pigments or color pigments, the latter being able to be divided into inorganic pigments and organic pigments. If used, all of the pigments mentioned are preferably finely divided, i.e. with average particle sizes of 100 μm and well below.

In order to achieve the formation of a uniform and as thin as possible coating, it is preferred to atomize the solution or dispersion of the coating materials as finely as possible before it hits the molded body. Processes according to the invention, in which the solution and / or dispersion in question is applied to the molded body via a nozzle, the mean droplet size in the spray mist being less than 100 μm, preferably less than 50 μm and in particular less than 35 μm, are preferably On in this way, the preferred thickness of the coating mentioned above can be easily realized. Another object of the present invention is the use of polymers or polymer mixtures for coating detergent and cleansing moldings, the polymer or at least 50% by weight of the polymer mixture being selected from

a) water-soluble nonionic polymers from the Grappe of

al) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the group of

b 1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide VA acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of

c 1) Acrylamidoalkyltrialkylammoniumchloride acrylic acid copolymers and their alkali and ammonium salts c2) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers

d) water-soluble anionic polymers from the Grappe group

dl) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide tepolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid

Methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the non-ionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinked d6) Copolymerization of at least one monomer from each of the following three

Copolymers obtained from Grappen: d6i) esters of unsaturated alcohols and short-chain saturated

Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, d6ii) unsaturated carboxylic acids, dόiii) esters of long-chain carboxylic acids and unsaturated alcohols and or esters from the carboxylic acids of Grappe d6ii) with saturated or unsaturated, straight-chain or branched C ₈ -ι ₈ -

Alcohol d7) Teφolymers of crotonic acid, vinyl acetate and an allyl or

Methallyl esters d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters d8iv) vinyl ether, vinyl ester or straight-chain allyl or methallyl ester d9) crotonic acid copolymers with one or more monomers from the

Grappe ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts dlO) Teφolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the group of

el) quaternized cellulose derivatives e2) polysiloxanes with quaternary grapple e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate6) Vinylpyrrolidone-methoimidazolinium chloride copolymers el) quaternized polyvinyl alcohol e8) under the INCI names Polyquatemium 2, Polyquatemium 17,

Polyquatemium 18 and Polyquatemium 27 indicated polymers.

This inventive use of the polymers mentioned leads to coated shaped bodies with advantageous properties, as the examples below show. With regard to preferred embodiments of the use according to the invention (ingredients, composition of the premix, preferred polymers etc.), what has been said above for the method according to the invention applies analogously. Examples:

For the production of uncoated detergent tablets, a surfactant granulate was mixed with other preparation components and pressed to form tablets on an eccentric tablet press. The composition of the surfactant granules is given in Table 1 below, the composition of the premix to be treated (and thus the composition of the shaped bodies) can be found in Table 2.

Table 1: Surfactant granules [% by weight]

Table 2: Premix [% by weight>]

** Terephthalic acid-ethylene glycol-polyethylene glycol ester (Rhodia, Rhόne-Poulenc)

The tablettable premix was pressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g).

These tablets were divided into three series, the first series of which, untreated, served as comparative example (V), while the second series (El) was sprayed with a 20% by weight solution of a polyvinylpyrrolidone / polyvinyl acetate copolymer in ethanol / water. The third series (E2) was sprayed with a solution of polyvinylpyrrolidone / vinyl alcohol copolymer and butylaminoethyl methacrylate in water / isopropanol. In both cases El and E2, dimethyl ether served as a blowing agent for the dispersions, which were atomized to a droplet size of 30 μm. In the case of example El, 150 mg of the polymer were applied as a coating, corresponding to a ratio of uncoated molded body to coating of 250 to 1. In example E2 according to the invention, 100 mg of polymer were applied (corresponding to a ratio of uncoated molded body to coating of 375 to 1). and the experiment is repeated with only 50 mg of polymer (E2 ', corresponding to a ratio of uncoated molded body to coating of 750 to 1).

Two tablets from each of the three series V, El and E2 were placed on a sieve with a 4 mm mesh size and shaken on a Retsch sieving machine at the highest amplitude for 120 seconds. After this experiment, the weight loss of the tablets was determined. The following Table 3 shows the weight loss of the molded body El, E2 and V, the values being mean values from five determinations.

To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely. The experimental data of the individual tablet series is shown in Table 3: Table 3: Detergent tablets [physical data]

The results show that the abrasion can be significantly reduced even with extremely small amounts of coating material without affecting the disintegration time.

Claims

claims

1. Washing and cleaning agent molded body made of compressed particulate washing and cleaning agent, containing builders (e), surfactant (s) and optionally further washing and cleaning agent components, characterized in that the molded bodies are coated with a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture is selected from

a) water-soluble nonionic polymers from the group of

al) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the Grappe

b 1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of cl) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride, methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

dl) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide teφolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone or in a mixture, copolymerized with crotonic acid, acrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) by copolymerization at least of a monomer of each of the following three groups of copolymers obtained: d6i) esters of unsaturated alcohols and short-chain saturated

Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, dόii) unsaturated carboxylic acids, dόiii) esters of long-chain carboxylic acids and unsaturated alcohols and or esters from the carboxylic acids of Grappe dόii) with saturated or unsaturated, straight-chain or branched C ₈ -ι ₈ -

Alcohol d7) Teφolymers of crotonic acid, vinyl acetate and an allyl or

Methallylester d8) tetra and pentapolymers d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate d8iii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters d9) crotonic acid copolymers with one or more monomers from the

Group ethylene, vinylbenzene, vinylmethylether, acrylamide and their water-soluble salts dlO) Teφolymers from vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the Grappe

el) quaternized cellulose derivatives e2) polysiloxanes with quaternary grapple e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate6) Vinylpyrrolidone-methoimidazolinium chloride copolymers el) quaternized polyvinyl alcohol e8) under the INCI names Polyquatemium 2, Polyquatemium 17,

Polyquatemium 18 and Polyquatemium 27 indicated polymers.

2. Detergent and molded article according to spoke 1, characterized in that the weight ratio of uncoated molded article to coating is greater than 100 to 1, preferably greater than 250 to 1 and in particular greater than 500 to 1.

3. Detergent and molded article according to one of claims 1 or 2, characterized in that the thickness of the coating on the molded article is 0.1 to 150 μm, preferably 0.5 to 100 μm and in particular 5 to 50 μm.

4. Detergent and molded article according to one of claims 1 to 3, characterized in that the coating in addition to the polymers mentioned polyurethanes in amounts of 5 to 50 wt .-%>, preferably from 7.5 to 40 wt .-% and contains in particular from 10 to 30% by weight, in each case based on the coating.

5. Detergent and molded article according to one of claims 1 to 4, characterized in that it additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight. , preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight, preferred disintegration aids having average particle sizes above 300 μm, preferably above 400 μm and in particular above 500 µm.

6. Detergent form according to one of claims 1 to 5, characterized in that they contain anionic (s) and / or nonionic (s) surfactant (s) and total surfactant contents above 2.5 wt .-% o, preferably above 5% by weight and in particular above 10% by weight, in each case based on the molded body weight.

7. Process for the production of coated washing and cleaning agent shaped bodies by known compression of a particulate washing and cleaning agent composition and subsequent immersion in or spraying with a melt, solution or dispersion of one or more polymers from the grapple

a) water-soluble nonionic polymers from the Grappe of al) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the group of

b 1) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids b8iii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the Grappe

cl) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts c2) acrylamidoalkyltrialkylammonium chloride, methacrylic acid copolymers and their alkali and ammonium salts c3) methacroylethylbetaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

dl) vinyl acetate / crotonic acid copolymers d2) vinylpyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide particles d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or

Methacrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) by copolymerization at least one monomer from each of the following three

Copolymers obtained from Grappen: d6i) esters of unsaturated alcohols and short-chain saturated

Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, dόii) unsaturated carboxylic acids, dόiii) esters of long-chain carboxylic acids and unsaturated alcohols and or esters from the carboxylic acids of Grappe dόii) with saturated or unsaturated, straight-chain or branched C ₈ _ι ₈ -

Alcohol d7) Teφolymers of crotonic acid, vinyl acetate and an allyl or

Methallylester d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters with one or more copolymers of d9) crotonic acid

Grappe ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts dlO) Teφolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in the α-position

e) water-soluble cationic polymers from the group of

el) quaternized cellulose derivatives e2) polysiloxanes with quaternary grapple e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate6) Vinylpyrrolidone-methoimidazolinium chloride copolymers e7) quaternized polyvinyl alcohol e8) under the INCI names Polyquatemium 2, Polyquatemium 17,

Polyquatemium 18 and Polyquatemium 27 indicated polymers.

8. The method according spoke 7, characterized in that an aqueous solution of one or more polymers from grappa a) to e) is sprayed onto the molded body, the aqueous solution, in each case based on the solution, 1 to 20 wt .-% , preferably 2 to 15% by weight and in particular 4 to 10% by weight> polymer (s) from groups a) to e), optionally up to 20% by weight>, preferably up to 10% by weight > and in particular below 5% by weight of one or more water-miscible solvents and the balance water.

9. The method according to any one of claims 7 or 8, characterized in that an aqueous dispersion of one or more polyurethanes, which additionally contains one or more dissolved polymers from groups a) to e), is sprayed onto the molded body, the dispersion, each based on the dispersion, 1 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight> polyurethane (s), 1 to 20% by weight, preferably 2 to 15% by weight .-% and in particular 4 to 10 wt .-% polymer (s) from grappa a) to e), optionally up to 20 wt .-%>, preferably up to 10 wt .-%> and in particular less than 5 wt .-% of one or more water-miscible solvents and the rest water.

10. The method according spoke 7, characterized in that a solution or dispersion of one or more polymers from the grappa a) to e) in a solvent or solvent mixture from the grappa water, ethanol, propanol, iso-propanol, n-heptane and whose mixtures are sprayed onto the moldings with the aid of inert blowing agents from the Grappe nitrogen, nitrous oxide, propane, butane, dimethyl ether and their mixtures.

11. The method according spoke 10, characterized in that the solution or dispersion has the following composition:

iv) 30 to 99% by weight, preferably 40 to 90% by weight and in particular 50 to 85

% By weight> ethanol, propanol, isopropanol, n-heptane or mixtures thereof, v) 0 to 20, preferably 1 to 15 and in particular 2 to 10% by weight> water, vi) 1 to 50, preferably 2 up to 25 and in particular 3 to 10% by weight. one or more polymers from grappa a) to e).

12. The method according to any one of claims 7 to 11, characterized in that the solution and / or dispersion in question is applied via a nozzle to the molded body, the average droplet size in the spray less than 100 microns, preferably less than 50 microns and in particular less than 35 μm.

13. The method according to any one of claims 7 to 12, characterized in that the molded body to be coated is obtained by pressing a particulate premix containing the surfactant-containing granules (s) and a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular at least 700 g / 1.

14. The method according spoke 13, characterized in that the surfactant-containing granules particle sizes between 100 and 2000 microns, preferably between 200 and 1800 μm, particularly preferably between 400 and 1600 μm and in particular between 600 and 1400 μm.

15. The method according to any one of claims 13 or 14, characterized in that the surfactant-containing granules contains anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10 wt .-%>, preferably at least 20 wt .-% and in particular at least 25% by weight.

16. The method according to any one of claims 13 to 15, characterized in that the particulate premix additionally one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils , Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

17. Use of polymers or polymer mixtures for the coating of detergent and cleaning product bodies, the polymer or at least 50% by weight of the polymer mixture being selected from

a) water-soluble nonionic polymers from the group of

al) polyvinylpyrrolidones, a2) vinylpyrrolidone / vinyl ester copolymers, a3) cellulose ethers

b) water-soluble amphoteric polymers from the Grappe

bl) alkyl acrylamide / acrylic acid copolymers b2) alkyl acrylamide / methacrylic acid copolymers b3) alkyl acrylamide / methyl methacrylic acid copolymers b4) alkyl acrylamide V acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers b5) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b6) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid

Copolymers b7) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers b8) copolymers from b8i) unsaturated carboxylic acids b8ii) cationically derivatized unsaturated carboxylic acids bδiii) optionally further ionic or nonionic monomers

c) water-soluble zwitterionic polymers from the group of

c 1) Acrylamidoalkyltrialky lammoniumchloriαVAacrylic acid copolymers and their alkali and ammonium salts c2) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts c3) Methacroylethylbetaine / methacrylate copolymers

d) water-soluble anionic polymers from the group of

dl) vinyl acetate / crotonic acid copolymers d2) vinyl pyrrolidone / vinyl acrylate copolymers d3) acrylic acid / ethyl acrylate / N-tert-butyl acrylamide teφolymers d4) graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone or in a mixture, copolymerized with crotonic acid, acrylic acid with polyalkylene oxides and / or polyalkylene glycols d5) grafted and crosslinked copolymers from the copolymerization of d5i) at least one monomer of the nonionic type, d5ii) at least one monomer of the ionic type, d5iii) of polyethylene glycol and d5iv) a crosslinker d6) copolymers obtained by copolymerizing at least one monomer of each of the following three groups: dόi) esters of unsaturated alcohols and short-chain saturated ones

Carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, dόii) unsaturated carboxylic acids, dόiii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of Grappe dόii) with saturated or unsaturated, straight-chain or branched C ₈ - ₁₈ -

Alcohol d7) Teφolymers of crotonic acid, vinyl acetate and an allyl or

Methallyl esters d8) tetra- and pentapolymers from d8i) crotonic acid or allyloxyacetic acid d8ii) vinyl acetate or vinyl propionate dδiii) branched allyl or methallyl esters d8iv) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters with one or more copolymers of graotonic acid from d9) crotonic acid , Vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts dlO) Teφolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic branched in the α-position monocarboxylic acid

e) water-soluble cationic polymers from the group of

el) quaternized cellulose derivatives e2) polysiloxanes with quaternary grapple e3) cationic guar derivatives e4) polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid e5) copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate e6) vinylpyπOlidone-methoimidazolinium chloride copolymers el) quaternized polyvinyl alcohol e8) under the INCI names Polyquatemium 2, Polyquatemium 17,

Polyquatemium 18 and Polyquatemium 27 indicated polymers.