EP1560913A2

EP1560913A2 - Water-soluble portion packaging with a filling

Info

Publication number: EP1560913A2
Application number: EP03811365A
Authority: EP
Inventors: Alexander Lambotte; Matthias Reimann
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2002-11-15
Filing date: 2003-11-07
Publication date: 2005-08-10
Also published as: AU2003302023A1; AU2003302023A8; DE10253213B3; WO2004045956A3; WO2004045956A2

Abstract

Aesthetically-pleasing washing or cleaning agent portions, combining the advantages of the compactness of tablets with the rapid solubility of portioned systems, comprise a water-soluble envelope with at least one core therein and a matrix of a pourable material, at least partly surrounding the core(s), whereby the core(s) is/are fixed to the water-soluble envelope.

Description

"Water-soluble portion packaging with filling"

The present invention is in the field of portioned compositions which preferably have washing and cleaning-active properties. Such detergent and cleaning agent portions include, for example, portioned agents for washing textiles, portioned detergents for machine dishwashing or cleaning hard surfaces, portioned bleaches for use in washing machines or dishwashers, portioned water softeners or stain salts; these individual forms of supply are summarized below under the term “detergent or cleaning agent portion”. In particular, the invention relates to washing and cleaning agent portions that are used for the automatic cleaning of dishes in household dishwashers.

Portioned detergents and cleaning agents are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. The portioning can be achieved, for example, by converting it into a compact form or by separate packaging. In the former case, tableting has an outstanding role; in the latter case, in the area of detergents or cleaning agents, mainly portions are used which are surrounded by packaging made of water-soluble materials.

Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages during storage and transport. Detergent tablets are consequently also extensively 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 consequently a 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 shaped bodies has the further disadvantage that many washing and cleaning agent shaped bodies cannot be washed in via the washing-in chamber of household washing machines, since the tablets do not disintegrate into secondary particles which are small enough to be washed into the washing drum from the washing-in chamber to become. This dichotomy between hardness (ie manageability) and decay only plays a subordinate role in packaged detergent or cleaning agent portions. Rather, phenomena such as the solubility or disintegrability of the packaging come to the fore, while the packaged detergent or cleaning agent only plays a role with its physical properties if a tablet has been packaged.

However, these portions have the disadvantage of not having the high degree of compactness that tablets have. The filling of tubular bags leads on the one hand to a low degree of compression, and on the other hand to a technically determined empty volume, so that a quantity of a detergent or cleaning agent measured for a washing or cleaning cycle takes up a larger space than a corresponding quantity in tableted form. In addition, the empty volume means that filled bags are unstable against mechanical influences and can burst.

In addition, filled tubular bags have little aesthetic appeal. The consumer only accepts this form of offer very little and does not trust the corresponding product to have a high level of performance. If only one uniform composition is packed in a bag, multifunctional advantages of the agents cannot be visualized.

In addition, there is the problem that the lower density of the portioned packaged compositions compared to tablets can lead to space problems in metering devices in dishwashers. Here it may be necessary to dose less so that the portion can be applied, which leads to poorer cleaning results.

The prior art therefore discloses packaging made of water-soluble materials which are not in the form of tubular bags but are produced by processes such as injection molding or deep drawing. These more rigid bodies are filled - similar to yoghurt cups - and sealed after filling. However, if you want to fill larger packagings for visualization of a multi-use in such packaging and surround them with another composition (e.g. a powder, a liquid or a melt), the pack can separate in an uncontrolled manner, which leads to problems with the closure of the filled hollow articles and to leads to aesthetic inconvenience.

The object of the present invention was to provide aesthetically appealing detergent or cleaning agent portions which combine the advantages of the compactness of tablets with those of the quick solubility of portioned systems. Larger solid bodies (“cores”), ie solid bodies, which differ significantly in size from particulate, should be used Lift off compositions and have, for example, minimum diameters above 2 mm, can be incorporated without causing technical or aesthetic disadvantages.

It has now been found that cores can be introduced into water-soluble portion packs and can be surrounded with flowable material if they are fixed to the water-soluble casing before being filled with flowable material.

In a first embodiment, the present invention relates to a portion packaging comprising a water-soluble envelope and at least one core located therein and a matrix of flowable material at least partially surrounding the core (s), in which the core (s) on the water-soluble covering is / are fixed.

In the following description of the invention, the terms “portion packaging” and “detergent or cleaning agent portion” are used without, where “detergent or cleaning agent portion” stands, other portion packaging according to the invention is not to be excluded. Rather, the portion packaging according to the invention is also suitable for others Areas of application such as pesticides, pharmaceuticals, cosmetics, etc.

The portion packaging according to the invention initially comprises a water-soluble envelope. This envelope can consist of a single material or a blend of different materials. In preferred portion packs according to the invention, the water-soluble wrapper comprises one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinyl pyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof. Optionally, plasticizers known to those skilled in the art can be added to the coverings to increase the flexibility of the material.

In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. "Polyvinyl alcohols" (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure

which in small proportions (approx. 2%) also structural units of the type

contain.

Commercial polyvinyl alcohols, which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups. The manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. Polyvinyl alcohol is largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through.

Portion packs preferred in the context of the present invention are characterized in that the water-soluble covering comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and is in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used, with portion packs according to the invention being preferred in which the water-soluble envelope comprises polyvinyl alcohols and / or PVAL copolymers, the molecular weight of which is particularly preferably in the range from 3,500 to 100,000 gmol ^"1 , preferably from 10,000 to 90,000 gmol ^" from 12,000 to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^{" 1} .

The degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500. Portion packs preferred according to the invention are characterized in that the water-soluble covering comprises polyvinyl alcohols and / or PVAL copolymers, the average degree of polymerization of which is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio MG (50 %) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

In summary, portion packs according to the invention are preferred in which the wrapping comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% %, with polyvinyl alcohols and / or PVAL copolymers being preferred, whose molecular weight is in the range from 3,500 to 100,000 gmol ^"1 , preferably from 10,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to 80,000 gmol ^"1 and in particular from 13,000 to 70,000 gmol ^"1 and particularly preferred polyvinyl alcohols and / or PVAL copolymers have an average degree of polymerization between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio MG (50%) to MG (90% ) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols which are particularly suitable as materials for the water-soluble coating can be found in the table below:

Other polyvinyl alcohols suitable as material for the water-soluble coating are ELVANOL ^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK). ERKOL types from Wacker are also suitable.

Another preferred group of water-soluble polymers that can serve as a coating according to the invention are the polyvinylpyrrolidones. These are sold, for example, under the name Luviskol ^® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)

which are produced 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. 2500-750000 g / mol, which are characterized by 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. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Also suitable are copolymers of vinylpyrrolidone with other monomers, in particular vinylpyrrolidone / Vinylester copolymers, as are marketed, for example 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 ₉ - CH -

² I o

I O R (ii)

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

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)

Other suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are briefly referred to as PEG. PEG are polymers of ethylene glycol which have the general formula (III)

H- (0-CH ₂ -CH ₂ ) _n -OH (III)

are sufficient, where n can have values between 5 and> 100,000.

PEGs are manufactured industrially by anionic ring opening polymerization of ethylene oxide (oxirane), usually in the presence of small amounts of water. Depending on how the reaction is carried out, they have molar masses in the range of approximately 200-5,000,000 g / mol, corresponding to degrees of polymerization of approximately 5 to> 100,000.

The products with molar masses <approx. 25,000 g / mol are liquid at room temperature and are referred to as the actual polyethylene glycols, abbreviation PEG. These short chain PEGs can in particular be other water soluble polymers e.g. Polyvinyl alcohols or cellulose ethers can be added as plasticizers. The polyethylene glycols which can be used according to the invention and are solid at room temperature are referred to as polyethylene oxides, abbreviation PEOX. High molecular weight polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and therefore only show weak glycol properties.

According to the invention, gelatin is also suitable as a water-soluble coating material, which is preferably used together with other polymers. Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily produced by hydrolysis of the skin and Bones from collagen contained in animals is obtained under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

Further water-soluble polymers which are suitable as coatings according to the invention are described below:

Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and

Methylhydroxypropylcellulose, such as are for example sold under the trademark Culminal® ^® and Benecel ^® (AQUALON). Cellulose ethers can be described by the general formula (IV)

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. Commercially available 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. Preferred portion packs according to the invention are characterized in that the water-soluble envelope comprises hydroxypropylmethyl cellulose (HPMC), which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9 , and has a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers that contain both free amino groups and free -COOH or S0 ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^" - or -S0 ₃ ^" groups, and summarized those polymers which contain -COOH or S0 ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is that available under the name Amphomer ^® acrylic resin which is a copolymer of tert-butylaminoethyl methacrylate, N- (1, 1, 3,3- tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally further ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen. Terpolymers 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 those available under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

Suitable water-soluble anionic polymers 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 (V):

[-CH (CH ₃ ) -CH (COOH) -] _n (V) 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 terpolymers, 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 in a mixture with other copolymerizable compounds on polyalkylene glycols, are obtained by polymerization in the heat in a homogeneous phase by the polyalkylene glycols being converted into the monomers of the vinyl esters, esters of acrylic acid or methacrylic acid 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 have 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-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are available.

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

H- (0-CH-CH ₂ ) _n -OH (VI)

I CH ₃

are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Technically important here are in particular 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 grafted onto polyethylene glycols 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 among them: 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-hexene.

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 particularly preferably contained in the graft polymers.

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

The grafted and crosslinked copolymers described above are preferably formed from: i) 5 to 85% by weight of 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 crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii) is. copolymers obtained by copolymerization of at least one monomer of each of the following three groups: i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or

Esters of short-chain sucked 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 .8 ₈ alcohols Among short-chain carboxylic acids or alcohols are to be understood as meaning those with 1 to 8 carbon atoms, where the carbon chains of these compounds can optionally be interrupted by double-bonded hetero groups such as -O-, -NH-, -S_.

Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester

These terpolymers contain monomer units of the general formulas (II) and (IV)

(see above) and monomer units from one or more allyl or methallyesters of the formula VII: R ¹ R ^; 3

R, 2 "-CC (0) -0-CH ₂ - C = CH ₂ (VII)

CH ₃

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 terpolymers 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

Methallyletsre of formula VII.

Tetra- and pentapolymers from 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 consisting of ethylene,

Vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts

Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic in

G position branched monocarboxylic acid.

Further polymers which can preferably be used according to the invention as a covering are cationic polymers. The permanent cationic polymers are preferred among the cationic polymers. According to the invention, "permanently cationic" means those polymers which have a cationic group irrespective of the pH. These are generally polymers which contain a quaternary nitrogen atom, for example in the form of an ammonium group. 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 those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® -Quat 3270 and 3272 (manufacturer: Th. Gold schmidt; di-quaternary polydimethylsiloxanes, Quatemium-80), Cationic guar derivatives, such as in particular the products lent 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 (dimethyldiallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.

Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as, for example, vinylpyrrolidone-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.

In addition to the water-soluble polymer or the water-soluble polymers, the coating of the detergent or cleaning agent portions according to the invention can contain further ingredients, which in particular improve the processability of the starting materials for the coating. Plasticizers and release agents are particularly worth mentioning here. In addition, dyes and / or fragrances and optical brighteners can be incorporated into the water-soluble coating in order to achieve aesthetic and / or technical effects there. According to the invention, in particular hydrophilic, high-boiling liquids can be used as plasticizers, it being possible, if appropriate, to use solids as a solution, dispersion or melt even at room temperature. Particularly preferred plasticizers come from the group consisting of glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, dodecaethylene glycol, glycerin, neopentyl glycol, trimethylol propane, pentaerythritol, mono -, Di-, triglycerides, surfactants, especially nonionic surfactants, and mixtures thereof.

Ethylene glycol (1, 2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, strongly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1, 113. The solidification point of ethylene glycol is - 11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is obtained from ethylene oxide by heating with water under pressure, and promising production processes can also be based on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.

Diethylene glycol (2,2'-oxydiethanol, digol), HO- (CH ₂ ) ₂ -0- (CH ₂ ) ₂ -OH, is a colorless, viscous, hygroscopic, sweet-tasting liquid, density 1, 12, which at -6 ° C melts and boils at 245 ° C. Diglycol is miscible in any ratio with water, alcohols, glycol ether, ketones, esters, chloroform, but not with hydrocarbons and oils. The diethylene glycol, usually called diglycol in practice, is made from ethylene oxide and ethylene glycol (ethoxylation) and is thus practically the starting link for polyethylene glycols (see above).

Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1, 261 that solidifies at 18.2 ° C. Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the W0 ₃ contact via the glycide stage.

Trimethylolpropane [TMP, Etriol, Ettriol, 1, 1, 1-Tris (hydroxymethyl) propane] is chemically exactly designated 2-ethyl-2-hydroxymethyl-1, 3-propanediol and comes in the form of colorless, hygroscopic masses with a melting point of 57 -59 ° C and a boiling point of 160 ° C (7 hPa) in the trade. It is soluble in water, alcohol, acetone, but insoluble in aliphatic and aromatic hydrocarbons. It is produced by reacting formaldehyde with butyraldehyde in the presence of alkalis.

Pentaerythritol [2,2-bis (hydroxymethyl) -1, 3-propanediol, penta, PE] is a white, crystalline powder with a sweet taste that is not hygroscopic and flammable and has a density of 1,399. has a melting point of 262 ° C and a boiling point of 276 ° C (40 hPa). Pentaerythritol is readily soluble in boiling water, slightly soluble in alcohol and insoluble in benzene, carbon tetrachloride, ether, petroleum ether. Technically, pentaerythritol is produced by reacting formaldehyde with acetaldehyde in an aqueous solution of Ca (OH) ₂ or NaOH at 15-45 ° C. First, a mixed aldol reaction takes place, in which formaldehyde reacts as the carbonyl component and acetaldehyde as the methylene component. Due to the high carbonyl activity of formaldehyde, the reaction of acetaldehyde with itself almost does not occur. Finally, the tris (hydroxymethyl) acetaldehyde thus formed is converted into pentaerythritol and formate with formaldehyde in a crossed Cannizzaro reaction.

Mono-, di-, triglycerides are esters of fatty acids, preferably longer-chain fatty acids with glycerin, one, two or three OH groups of the glycerol being esterified, depending on the type of glyceride. Examples of suitable acid components with which the glycerol can be esterified in mono-, di- or triglycerides which can be used as plasticizers are hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), Undecanoic acid etc. In the context of the present compound, preference is given to the use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetraeric acid (locanoic acid) , Hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselaidic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (Linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid). For reasons of cost, the native fatty substances (triglycerides) or the modified native fatty substances (partially hydrolyzed fats and oils) can also be used directly. Alternatively, fatty acid mixtures can also be prepared by cleaving native fats and oils and then separated, the purified fractions later being converted into mono-, di- or triglycerides. Acids are esterified with the Glacerin here, coconut oil fatty acid (in particular, about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% C _14, 10 percent .-% C _16, 2 wt .-% _C18, 8 wt .-% C ₁₈ - 1 wt .-% Cι ₈ -), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C ₁₀ , 50% by weight C ₁₂ , 15% by weight C ₁₄ , 7% by weight C ₁₆ , 2% by weight C ₁₈ , 15% by weight C ₁₈ -, 1% by weight C ₁₈ -), tallow fatty acid (approx. 3% by weight C ₄ , 26% by weight C ₁₆ , 2% by weight C ₁₆ -, 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44 % By weight C ₁₈ -, 3% by weight C ₁₈ ^» , 1% by weight C ₁₈ -). Hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight C ₁₇ , 63% by weight C ₁₈ , 1% by weight Cι ₈ -), technical oleic acid ( about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt .-% C ₁₆ - 1 wt .-% C _17, 2 wt .-% C ₁₈ , 70% by weight C ₁₈ -, 10% by weight C ₁₈ -, 0.5% by weight C _1β -), technical palmitin / stearic acid (approx. 1% by weight C ₁₂ , 2% by weight % C ₁₄ 45 wt .-% C _16, 2 wt .-% C _17, 47 wt % C ₁₈ , 1% by weight C ₁₈ -) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C ₁₈ - , 45% by weight C ₁₈ ^» , 7% by weight C ₁₈ -).

Surfactants, in particular nonionic surfactants, are also suitable as further plasticizers. 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 residue 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. The preferred ethoxylated alcohols include, for example, C _2-1 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C. _12- ι ₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and _C12-18 alcohol containing 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

It is particularly preferred to use nonionic surfactants which have a melting point above room temperature as plasticizers. Accordingly, preferred coatings are characterized in that non-ionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, are used as plasticizers , 3 ° C, can be used.

Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.

Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. In a preferred embodiment of the present invention, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.

A particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _{_16-2} alcohol), a C preferably ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and in particular at least 20 moles of ethylene oxide won. Among these, the so-called "narrow ranks ethoxylates" (see above) are particularly preferred.

Accordingly, in particularly preferred processes according to the invention, ethoxylated nonionic surfactant (s) are used which consist of C _6-20 monohydroxyalkanols or C ₆ . ₂ o-alkyl phenols or C ₆ - ₂ o-fatty alcohols and more than 12 mol, preferably more than 15 mol and was recovered in particular more than 20 moles of ethylene oxide per mole of alcohol (s).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.

Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight. -% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Further preferred nonionic surfactants satisfy the formula

R ¹ 0 [CH ₂ CH (CH ₃ ) 0] _x [CH ₂ CH ₂ 0] _y [CH ₂ CH (0H) R ² ], in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or - CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula can be used

R ¹ 0 [CH ₂ CH (R ³ ) 0] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 represents} H and x assumes values from 6 to 15.

Further substances which can preferably be used as plasticizers are glycerol carbonate, propylene glycol and propylene carbonate.

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is reacted under pressure in the presence of catalysts with CO ₂ to give glycerol carbonate. Glycerol carbonate is a clear, easily movable liquid with a density of 1, 398 ^"3 , which boils at 125-130 ° C (0.15 mbar).

There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3-propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet-tasting liquid with a density of 1, 0597 that solidifies at -32 ° C and boils at 214 ° C. 1,3-propanediol can be prepared from acrolein and water with subsequent catalytic hydrogenation.

Technically far more important is 1, 2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1, 0381, which solidifies at -60 ° C and boils at 188 ° C. 1, 2-propanediol is made from propylene oxide by adding water.

Propylene carbonate is a water-bright, easily movable liquid with a density of 1, 21 like ^"3 , the melting point is -49 ° C, the boiling point is 242 ° C. Propylene carbonate is also available on an industrial scale due to the reaction of propylene oxide and C0 ₂ at 200 ° C and 80 bar accessible.

Highly disperse silicas are particularly suitable as additional additives, which are preferably in solid form at room temperature. Pyrogenic silicas such as the commercially available Aerosil ^® or precipitated silicas are available here. Particularly preferred processes according to the invention are characterized in that one or more materials from the group (preferably highly disperse) silica, dispersion powder, high molecular weight polyglycols, stearic acid and / or stearic acid salts, and / or from the group of inorganic salts such as sodium sulfate, calcium chloride and / or from the group of inclusion formers such as urea, cyclodextrin and / or from the group of Superadsorbers such as (preferably crosslinked) polyacrylic acid and / or their salts such as Cabloc 5066 / CTF and mixtures thereof are / are used.

The water-soluble coating can be obtained from the above-mentioned materials or their mixtures by injection molding or blow molding. The casting can take place both from the melt and from a solution with subsequent drying. Other methods for shaping plastics processing are also suitable. For reasons of process economy, however, it is preferred that the water-soluble wrapping of the portion packaging according to the invention is formed from a film material whose thickness is 10 to 1000 μm, preferably 20 to 750 μm and in particular 30 to 500 μm.

As a further constituent, the portion packs according to the invention contain a “core”, that is to say a solid body whose size clearly stands out from particulate compositions. Preferred cores have, for example, minimum diameters above 2 mm, with cores being preferred, the masses above 200 mg, particularly preferably have above 500 mg and in particular above 1 g.

The cores can be produced using the usual manufacturing processes for solids, preferably by tableting. Portion packaging according to the invention in which the core is a tablet is preferred here. In tablet-coated cores, all common tablet shapes and types can be used, so that, for example, two-layer cores with different layer compositions can also be produced.

Alternatively, cores can also be produced by casting and subsequent solidification. Portion packaging according to the invention in which the core is a solidified melt is preferred here. Of course, there are no limits to the creativity of the product designer, so that cores as well, which combinations of tableted components and possibly cast-in parts can be used according to the invention.

If it is desired to process liquids for material, manufacturing or aesthetic reasons, cores can also be used which contain liquid in an envelope. In addition to injection molded or blow molded parts, gelatin capsules are particularly suitable here.

According to the invention, the portion packaging contains at least one core. The description below does not always explicitly indicate that the packaging also contains several May contain cores. The use of the singular in the illustration below is therefore not to be understood as limiting.

The core is fixed to the water-soluble coating according to the invention. In addition to the fixation, the core can be surrounded by walls or compartmentalization devices in such a way that it is delimited by at least one area of the water-soluble covering. This procedure creates several compartments in which incompatible ingredients can be present without reacting with each other. Corresponding portion packaging according to the invention, in which the core is spatially delimited by an internal web or a weir, is preferred.

The core or cores can be fixed in different ways. For example, it is possible to form a positive or clamping connection between the water-soluble casing and the core. One possibility for this is that the core is fixed to the water-soluble covering by positioning the core in a shaped cavity of the covering.

For reasons of process economy, it may be preferred to drop the core into a depression in the casing, whereby it penetrates into the depression due to its own weight. Adhesion in such a depression can then advantageously be achieved by shrinking the wrapping material around the core and thus tightly enclosing it. This type of fixation is preferred over the former because of the mechanically less complex core dosing. Portion packagings according to the invention are correspondingly preferred in which the core is fixed to the water-soluble wrapping by shrink-wrapping wrapping material.

As an alternative to the form or clamp connection or in addition to this, the core can also be fastened to the covering by means of an adhesive closure. Portion packaging according to the invention is preferred here, in which the core is fixed to the water-soluble envelope by an adhesive connection.

The adhesive connection can be achieved, for example, by moistening the location of the water-soluble packaging at which the core is used. As a result, the water-soluble coating is partially dissolved, whereby a highly concentrated polymer solution is generated quasi “in situ”, which can serve as an adhesion promoter. Of course, other adhesion promoters can also be used. Preferred materials for the adhesive bond are adhesives or so-called adhesion promoters. In the context of the present invention, preferred adhesion promoters are solutions, dispersions, emulsions or melts which have a viscosity below 3000 mPas.

In the context of the present invention, the viscosity values relate to viscosity measurements at a sample temperature which corresponds to the processing temperature of the adhesion promoter (s) (see below), using a Carrimed plate-plate rheometer, at a shear force of 50 N per square meter, a plate diameter of 5 cm and a measuring system gap of 250 μm, the value being read after a measuring time of 10 seconds.

Preferred adhesion promoters have a viscosity below 2500 mPas, preferably below 2000 mPas and in particular below 1000 mPas during processing.

The processing temperature of the adhesion promoter (s) depends on the material nature of the adhesion promoter used and the desired time within which the adhesion promoter is to develop its adhesive properties. Temperatures from room temperature (which in some cases can be 10 to 15 ° C in winter months) to high temperatures above the boiling point of water can be achieved. In the case of preferred methods of producing adhesive bonds in the context of the present invention, the adhesion promoters are metered into the cavity at a temperature between 10 and 130 ° C., preferably between 20 and 110 ° C. and in particular between 20 and 90 ° C.

The adhesion promoter (s) can be metered in as a melt, which can usually necessitate temperatures above 30 ° C., preferably above 40 ° C. and in particular above 50 ° C.

In the context of the present invention, particularly preferred fusible adhesion promoters are substances from the group of polyethylene and polypropylene glycols. Mixtures of substances containing these substances are also preferred. Adhesion promoters from the groups of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are accordingly preferred embodiments of the present invention.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are polymers of ethylene glycol which have the general formula

H- (0-CH ₂ -CH ₂ ) _n -OH are sufficient, where n can have values between 1 (ethylene glycol) and over 100,000. The decisive factor in evaluating whether a polyethylene glycol can be used according to the invention is the viscosity of the PEG at the processing temperature. Since the preferred processes work above 20 ° C and below 90 ° C, the polyethylene glycols of the above formula are particularly suitable, in which n assumes values between approximately 15 and approximately 150. The polyethylene glycols with higher molecular weights are polymolecular, ie they consist of groups of macromolecules with different molecular weights. 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. According to this nomenclature, the technically customary polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 can preferably be used in the context of the present invention.

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 above formula. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-32, PEG-40, PEG-55, PEG 60, PEG-75 and PEG-100 can preferably be used according to the invention.

Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 540 (Union Carbide), Emkapol ^® 2000 (ICI Americas), Lipoxol ^® 2000 MED (Huls America), polyglycol ^® E-1550 (Dow Chemical), Lutrol ^® E2000 (BASF) and the corresponding trade name with higher numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula

H- (0-CH-CH ₂ ) _n -OH

I CH ₃

are sufficient, where n values can be between 1 (propylene glycol) and approx. 1000. Similar to the PEG described above, the assessment of whether a polypropylene glycol can be used according to the invention depends on the viscosity of the PPG at the processing temperature. In the context of the present invention, the technically customary polypropylene glycols PPG 1550, PPG 3000, PPG 4000 and PPG 6000 can preferably be used.

Since the temperature control can be critical when metering melts, it is preferred to use solutions or dispersions of adhesion promoters which are solid at room temperature or emulsions of adhesion promoters which are liquid at room temperature according to the invention. Here, the emulsions have only a subordinate meaning because of later problems with the adhesion of the core. The dispersions are also less suitable because of the settling problem in processing in comparison with the particularly preferred solutions.

Particularly preferred adhesion promoters are solutions of certain nonionic substances. Solutions of polyhydric alcohols and / or sugars solid at room temperature are preferred as adhesion promoters, preference being given to solutions which, based on the solution, contain at least 30% by weight, preferably at least 40% by weight and in particular at least 50% by weight of solids (e) included.

Polyhydric alcohols in the context of the present invention are compounds which have at least two hydroxyl groups. The physical state of these compounds at room temperature (20 ° C) is fixed. Particularly suitable polyhydric alcohols are, for example, trimethylolpropane, pentaerythritol and the “sugar alcohols”, ie the polyhydroxy compounds formed from monosaccharides by reducing the carbonyl group. A distinction is made in these between the number of hydroxyl groups contained in the molecule, tetrites, pentites and hexites etc. Sugar alcohols which are particularly suitable in the context of the present invention are, for example, threit and erythritol, adonite (ribitol), arabitol (formerly: lyxitol) and xylitol, dulcitol (galactitol), mannitol and sorbitol (glucitol), the latter also is called sorbitol.

In the context of the present invention, the term “sugar” denotes single and multiple sugars, that is to say monosaccharides and oligosaccharides, in which 2 to 6 monosaccharides are linked to one another in the manner of acetals. In the context of the present invention, “sugars” are therefore monosaccharides, disaccharides, trisaccharides, tetrahydrosaccharides. , Penta and hexasaccharides.

Monosaccharides are linear polyhydroxy aldehydes (aldoses) or polyhydroxy ketones (ketoses). They usually have a chain length of five (pentoses) or six (hexoses) carbon atoms. Monosaccharides with more (heptoses, octoses, etc.) or fewer (tetrosen) carbon atoms are relatively rare. Monosaccharides sometimes have a large number of asymmetric carbon atoms. For a hexose with four asymmetric carbon atoms, this results in a number of 24 stereoisomers. The orientation of the OH group on the highest numbered asymmetr. C atom in the Fischer projection divides the monosaccharides into D and L-configured Rows. In the naturally occurring monosaccharides, the D configuration is far more common. If possible, monosaccharides form intramolecular hemiacetals, so that ring-like structures of the pyran (pyranoses) and furan type (furanoses) result. Smaller rings are unstable, larger rings are only stable in aqueous solutions. The cyclization creates another asymmetric carbon atom (the so-called anomeric carbon atom), which doubles the number of possible stereoisomers. This is indicated by the prefixes α- u. ß- expressed. The formation of hemiacetals is a dynamic process, which depends on various factors such as temperature, solvent, pH value, etc. Mixtures of both anomeric forms are usually present, sometimes also as mixtures of the furanose and pyranose forms.

Monosaccharides which can be used as sugar in the context of the present invention are, for example, the tetroses D (-) - erythrose and D (-) - threose and D (-) - erythrulose, the pentoses D (-) - ribose, D (-) - ribulose, D (-) - arabinose, D (+) - xylose, D (-) - xylulose as well as D (-) - lyxose and the hexoses D (+) - allose, D (+) - old rose, D (+) - glucose , D (+) - Mannose, D (-) - Gulose, D (-) - ldose, D (+) - Galactose, D (+) - Talose, D (+) - Psicose, D (-) - Fructose, D (+) - sorbose and D (-) - tagatose. The most important and most widespread monosaccharides are: D-glucose, D-galactose, D-mannose, D-fructose, L-arabinose, D-xyiosis, D-ribose and the like. 2-deoxy-D-ribose.

Disaccharides are made up of two simple monosaccharide molecules linked by glycosidic bonds (D-glucose, D-fructose, etc.). If the glycosidic bond lies between the acetal carbon atoms (1 for aldoses and 2 for ketoses) of both monosaccharides, the ring shape is fixed in both; the sugars show no mutarotation, do not react with ketone reagents and no longer have a reducing effect (Fehling negative: trehalose or sucrose type). If, on the other hand, the glycosidic bond connects the acetal carbon atom of one monosaccharide with any of the second, this can still assume the open-chain form, and the sugar has a reducing effect (Fehling positive: maltose type).

The main disaccharides are sucrose (cane sugar, sucrose), trehalose, lactose (milk sugar), lactulose, maltose (malt sugar), cellobiose (cellulose breakdown product), gentobiose, melibiose, turanose and others.

Trisaccharides are carbohydrates, which are made up of 3 glycosidically linked monosaccharides and for which one sometimes comes across the incorrect term triosen. Trisaccharides are relatively rare in nature, examples are gentianose, kestose, maltotriose, melecitose, raffinose, and as an example of trisaccharides containing streptomycin and validamycin containing aminosugars. Tetrasaccharides are oligosaccharides with 4 monosaccharide units. Examples of this class of compounds are stachyose, lychnose (galactose-glucose-fructose-galactose) and secalose (from 4-fructose units).

In the context of the present invention, saccharides from the group consisting of glucose, fructose, sucrose, cellubiosis, maltose, lactose, lactulose, ribose and mixtures thereof are preferably used as sugars. Detergent tablets which contain glucose and / or sucrose are particularly preferred.

A preferred adhesion promoter that can be used in the form of a solution is sorbitol. Processes according to the invention are preferred here, in which solutions of sorbitol are used as adhesion promoters which, based on the solution, contain at least 50% by weight, preferably at least 60% by weight and in particular at least 70% by weight of sorbitol.

Another preferred class of substances that can be used as an adhesion promoter in the form of their solution are water-soluble polyurethanes. Among them, certain representatives are particularly preferred. Processes according to the invention are preferred here in which solutions or suspensions of polyurethanes composed of diisocyanates (A) and diols (B) act as adhesion promoters.

0 = C = NR ¹ -N = C = 0 (A),

H-0-R ² -0-H (B),

are used, the diols being selected at least in part from polyethylene glycols (a) and / or polypropylene glycols (b)

H- (0-CH ₂ -CH ₂ ) _n -OH (a),

H- (0-CH-CH ₂ ) _n -OH (b),

CH ₃

and R ¹ and R ² independently of one another represent a substituted or unsubstituted, straight-chain or branched alkyl, aryl or alkylaryl radical having 1 to 24 carbon atoms and n each represent numbers from 5 to 2000.

These preferred polymers are described in more detail below. Polyurethanes are polyadducts of at least two different types of monomers, a di- or polyisocyanate (A) and a compound (B) with at least 2 active hydrogen atoms per molecule

The polyurethanes used as a solution or suspension or dispersion are obtained from reaction mixtures which contain at least one diisocyanate of the formula (A) and at least one polyethylene glycol of the formula (a) and / or at least one polypropylene glycol of the formula (b).

The reaction mixtures can additionally contain further polyisocyanates. It is also possible for the reaction mixtures - and therefore the polyurethanes - to contain other 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.

If additional diols etc. are added, certain quantitative ratios of the polyethylene and / or polypropylene glycol units which are mandatory in the polyurethane according to the invention must be observed. It is preferred here that at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight and in particular at least 75% by weight, of the diols reacted in the polyurethane are selected from polyethylene glycols (a) and / or polypropylene glycols (b).

The solution or dispersion or suspension of the adhesion promoter can contain, in addition to the special polyurethanes, further ingredients such as ingredients of detergents and cleaning agents, in particular colorants and / or fragrances.

The polyurethanes contain diisocyanates of the formula (AA) as a monomer unit. Hexamethylene diisocyanate, 2,4- and 2,6-toluenediisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate are predominantly used as diisocyanates. These compounds can be described by the formula (A) listed above, in which R ^{1 represents} a connecting group 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 ¹ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluenediisocyanate (TDI) R ¹ 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), and in isophorone diisocyanate R ^{1 represents} the isophorone residue (3,5,5-trimethyl-2-cyclohexenone) , The polyurethanes also contain diols of the formula (B) as a monomer unit, at least some of these diols originating from the group of polyethylene glycols (a) and / or polypropylene glycols (b). Polyethylene glycols are polymers of ethylene glycol which have the general formula (a)

H- (0-CH ₂ -CH ₂ ) _n -OH (a)

are sufficient (see above).

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

H- (0-CH-CH ₂ ) _n -OH (b)

I CH ₃

are sufficient, where n can have values between 5 and 2000.

Both in the case of compounds of the formula (a) and in the case of compounds of the formula (b), such representatives are preferred monomer units in which the number n is a number between 6 and 1500, preferably between 7 and 1200, particularly preferably between 8 and 1000 , more preferably between 9 and 500 and in particular between 10 and 200. For certain applications, polyethylene and polypropylene glycols of the formulas (II a) and / or (II b) may be preferred, in which n is a number between 15 and 150, preferably between 20 and 100, particularly preferably between 25 and 75 and in particular between 30 and 60 stands.

Examples of compounds optionally further contained in the reaction mixtures for the production of the polyurethanes are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, ethylene diamine, propylene diamine, 1,4-diaminobutane, hexamethylene diamine and α, ω-diamines based on long-chain Alkanes or polyalkylene oxides. Detergent tablets according to the invention in which the polyurethanes in the coating contain additional diamines, preferably hexamethylene diamine and / or hydroxycarboxylic acids, preferably dimethylolpropionic acid, are preferred.

Depending on which reactants are reacted with each other to form the polyurethanes, the result is polymers with different structural units. Here are inventive Process according to preferred, in which solutions or suspensions of polyurethanes are used which have structural units of the formula (C)

- [0-C (0) -NH-R ¹ -NH-C (0) -0-R ² ] _k - (C),

in which R ^{1 stands} for - (CH ₂ ) ₆ - or for 2,4- or 2,6-C ₆ H ₃ -CH ₃ , or for C ₆ H ₄ -CH ₂ -C ₆ H ₄ and R ² is selected from -CH ₂ -CH ₂ - (0-CH ₂ -CH ₂ ) _n - or -CH (CH ₃ ) -CH ₂ - (0-CH (CH ₃ ) -CH ₂ ) _π -, where n is a Number from 5 to 199 and k is a number from 1 to 2000.

The diisocyanates described as preferred can be reacted with all the diols described as preferred to give polyurethanes, so that in preferred processes according to the invention polyurethanes are used as adhesion promoters which have one or more of the structural units (C a) to (C h):

- [0-C (0) -NH- (CH ₂ ) ₆ -NH-C (0) -0-CH ₂ -CH ₂ - (0-CH ₂ -CH ₂ ) _n ] k- (C a),

- [0-C (0) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (0) -0-CH ₂ -CH ₂ - (0-CH ₂ -CH ₂ ) _n ] _k - (C b),

- [0-C (0) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (0) -0-CH ₂ -CH ₂ - (0-CH ₂ -CH ₂ ) _n ] _k - (C c),

- [0-C (0) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (0) -0-CH ₂ -CH ₂ - (0-CH ₂ -CH ₂ ) _n ] _k - (C d),

- [0-C (0) -NH- (CH ₂ ) ₆ -NH-C (0) -0- CH (CH ₃ ) -CH ₂ - (0-CH (CH ₃ ) -CH ₂ ) _n ] _k - (C e),

- [0-C (0) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (0) -0-CH (CH ₃ ) -CH ₂ - (0-CH (CH ₃ ) -CH ₂ ) _n ] _k - (C f),

- [0-C (0) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (0) -0-CH (CH ₃ ) -CH ₂ - (0-CH (CH ₃ ) -CH ₂ ) _n ] _k - (C g),

- [0-C (0) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (0) -0-CH (CH ₃ ) -CH ₂ - (0-CH (CH ₃ ) -CH ₂ ) n] _k - (C h),

where n is a number from 5 to 199 and k is a number from 1 to 2000.

As already mentioned above, the reaction mixtures can contain, in addition to diisocyanates (A) and diols (B), further compounds from the group of polyisocyanates (in particular triisocyanates and tetraisocyanates) and from the group of polyols and / or di- or polymains. In particular triols, tetrols, pentols and hexols as well as di- and triamines can be contained in the reaction mixtures. A content of compounds with more than two "active" H atoms (all classes of substances mentioned above with the exception of diamines) leads to a partial crosslinking of the polyurethane reaction products and can bring about advantageous properties such as, for example, control of the dissolution behavior, stability or flexibility of the adhesive connection, process advantages when metering, etc. The content of such compounds with more than two “active” H atoms in the reaction mixture is usually less than 20% by weight of the total reactants used for the diisocyanates, preferably less than 15% by weight and in particular less than 5% by weight. %.

In preferred embodiments of the present invention, the polyurethanes M have Moollmmaassseenn vvoonn 55000000 bbiiss 115500..000000 ggmmooll ^{"" 11} ,, preferably from 10,000 to 100,000 gmol ^"1 and in particular from 20,000 to 50,000 gmol ^{" 1} .

As a third component, the portion packs according to the invention have a matrix of flowable material, which is contained in the wrapper and at least partially surrounds the core (s). In the context of the present application, "flowable" means that the matrix can be introduced into the casing by simple metering processes. The term "flowable" thus expressly includes the terms "pourable" or "free-flowing".

In preferred embodiments of the present invention, the flowable material is a liquid or a flowable gel. Portion packs according to the invention are preferred here in which the flowable material is a liquid whose viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3) is preferably in the range from 500 to 50,000 mPas, more preferably from 1000 to 10,000 mPas, particularly preferably from 1200 to 5000 mPas and in particular from 1300 to 3000 mPas.

"Flowable" in the sense of the present invention are also matrices which can be processed fluently, but later lose the state of flowability, for example harden or solidify.

The flowable matrices can be cured by different mechanisms, the time-delayed water binding, cooling below the melting point, evaporation of solvents, crystallization, by chemical reaction (s), in particular polymerization, and the change in the rheological properties, e.g. due to changed shear of the mass (es), the most important hardening mechanisms besides radiation hardening by UV, alpha, beta or gamma rays or microwaves are to be mentioned.

The time-delayed water binding in the matrices can be realized in different ways. There are, for example, masses that can be hydrated, water-free raw materials or raw materials with low hydration levels, which can change into stable higher hydrates, and contain water. The formation of the hydrates, which does not occur spontaneously, then leads to the binding of free water, which in turn leads to hardening of the masses.

The time-delayed water binding can also take place, for example, by incorporating hydrate-containing salts, which dissolve in their own crystal water when the temperature rises, into the matrices. If the temperature drops later, the crystal water is bound again, which leads to a loss of formability with simple means and to a solidification of the matrices.

The swelling of natural or synthetic polymers as a time-delayed water binding mechanism can also be used according to the invention. Mixtures of unswollen polymer and suitable swelling agent, e.g. Water, diols, glycerin etc., are incorporated into the matrices, swelling and hardening taking place after metering.

The most important mechanism of curing through time-delayed water binding is the use of a combination of water and water-free or low-water raw materials that slowly hydrate. For this purpose, there are in particular substances which contribute to the cleaning performance in the washing or cleaning process. Ingredients of the matrices preferred according to the invention are, for example, phosphates, carbonates, silicates and zeolites.

It is particularly preferred if the hydrate forms formed have low melting points, since in this way a combination of the curing mechanisms is achieved by internal drying and cooling. It is preferred that the matrices contain 10 to 95% by weight, preferably 15 to 90% by weight, particularly preferably 20 to 85% by weight and in particular 25 to 80% by weight of anhydrous substances which are hydrated into a Change to hydrate form with a melting point below 120 ° C., preferably below 100 ° C. and in particular below 80 ° C.

Another mechanism for curing the matrices processed in accordance with the invention lies in the cooling when the matrices are processed above their softening point. Methods in which the deformable matrices are cured by cooling below the melting point are therefore preferred.

Masses softenable under the influence of temperature can be easily assembled by mixing the desired further ingredients with a meltable or softenable substance and heating the mixture to temperatures in the softening range of this substance and at these Temperatures is metered. Waxes, paraffins, polyalkylene glycols, etc., are particularly preferably used as meltable or softenable substances. These are described below.

The meltable or softenable substances should have a melting range (solidification range) in such a temperature range in which the other ingredients of the masses to be processed are not exposed to excessive thermal stress. In matrices preferred according to the invention, the meltable or softenable substances have a melting point above 30 ° C.

It has proven to be advantageous if the meltable or softenable substances do not show a sharply defined melting point, as is usually the case with pure, crystalline substances, but instead have a melting range that may include several degrees Celsius. The meltable or softenable substances preferably have a melting range which is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. The width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. 'Waxing' is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C without decomposition and which are relatively low-viscosity and non-stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility.

The waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, camauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes. Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as meltable or softenable substances.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides can also be used at least in part as a constituent of the meltable or softenable substances, but they can also be water-insoluble or only slightly water-soluble

Polyalkylene glycol.

Particularly preferred meltable or softenable substances in the materials to be processed are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), polyethylene glycols with molecular weights between 1500 and 36,000 being preferred, those with molecular weights from 2000 to 6000 being particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred. Corresponding processes which are characterized in that the plastically deformable mass (s) contain / contain at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are preferred. Here, compositions to be processed according to the invention are particularly preferred which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the only meltable or softenable substances. These substances have been described in detail above. In a further preferred embodiment, the matrices to be processed according to the invention predominantly contain paraffin wax. This means that at least 50% by weight of the total meltable or softenable substances contained, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total amount of meltable or softenable substances) of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, even higher proportions of, for example, more than 90% by weight. are particularly preferred.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline cleaning agent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if this melting temperature is not reached in the detergent fleet. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided.

Matrices to be processed preferably contain at least one paraffin wax with a melting range of 50 ° C to 60 ° C as meltable or softenable substances, preferred methods being characterized in that the deformable mass (es) is a paraffin wax with a melting range of 50 ° C to 55 ° C contains.

Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing proportion of solid wax components, the resilience of the process end products to impacts or friction on other surfaces increases, which leads to longer-lasting protection. High proportions of oils or liquid wax constituents can weaken the molded articles or molded article areas, which opens pores and exposes the active substances to the environmental influences mentioned at the beginning. In addition to paraffin, the meltable or softenable substances can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent. In a further preferred embodiment of the present invention, the mixture forming the meltable or softenable substances should be such that the mass and the molded body or molded body component formed therefrom are at least largely water-insoluble. The solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C. and should preferably be below 5 mg / l.

In such cases, however, the meltable or softenable substances should have the lowest possible solubility in water, even in water at an elevated temperature, in order to largely avoid a temperature-independent release of the active substances.

The principle described above serves to delay the release of ingredients at a certain point in the cleaning cycle and can be used particularly advantageously if the main rinse cycle is carried out at a lower temperature (for example 55 ° C.), so that the active substance from the rinse aid particles only in the rinse cycle at a higher level Temperatures (approx. 70 ° C) is released.

Preferred matrices to be used according to the invention are characterized in that, as meltable or softenable substances, they contain one or more substances with a melting range from 40 ° C to 75 ° C in amounts of 6 to 30% by weight, preferably 7.5 to 25% by weight .-% and in particular from 10 to 20 wt .-%, each based on the weight of the mass.

Another mechanism by which the matrices can be cured is the evaporation of solvents. For this purpose, solutions or dispersions of the desired ingredients can be prepared in one or more suitable, volatile solvents, which release these solvents after metering and harden in the process. Examples of suitable solvents are lower alkanols, aldehydes, ethers, esters, etc., the selection of which is made depending on the further composition of the matrices to be processed. Particularly suitable solvents for processes in which the deformable mass (s) are cured by evaporation of solvents are ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl 2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol and the acetic acid esters of the abovementioned alcohols, in particular ethyl acetate. The evaporation of the solvents mentioned can be accelerated by heating or by moving air. Combinations of the measures mentioned are also suitable for this purpose, for example blowing on with warm or hot air.

Another mechanism that can be the basis of hardening is crystallization.

Crystallization as the mechanism underlying hardening can be used, for example, by melting crystalline substances as the basis of one or more matrices. After processing, such systems go into a higher order state, which in turn leads to hardening of the entire molded body formed. However, crystallization can also be carried out by crystallization from supersaturated solution. In the context of the present invention, supersaturation is the term for a metastable state in which more of a substance is present in a closed system than is required for saturation. A supersaturated solution obtained, for example, by hypothermia therefore contains more solute than it should contain in thermal equilibrium. The excess of dissolved substance can be brought to instantaneous crystallization by seeding with germs or dust particles or by shaking the system. In the context of the present invention, the term “oversaturated” always refers to a temperature of 20 ° C. If a substance dissolves x grams per liter in a certain solvent at a temperature of 20 ° C, the solution in the context of the present invention is to be referred to as "supersaturated" if it contains (x + y) grams of the substance per liter , where y> 0 applies. In the context of the present invention, solutions are also to be referred to as "supersaturated" which serve as the basis of a matrix to be processed at an elevated temperature and are processed at this temperature at which there is more of a solute in the solution than at Would dissolve 20 ° C in the same amount of solvent.

The term "solubility" in the present invention means the maximum amount of a substance that the solvent can absorb at a certain temperature, i.e. the proportion of the solute in a solution saturated at the temperature in question. If a solution contains more solute than it should contain in the thermodynamic equilibrium at a given temperature (e.g. under hypothermia), it is called supersaturated. Vaccinating with germs can cause the excess to precipitate out as the bottom of the now only saturated solution. However, a solution saturated with one substance can also dissolve other substances (e.g. you can still dissolve sugar in a saturated saline solution).

As described above, the state of supersaturation can be achieved by slow cooling or by subcooling a solution as long as the solute in the solvent higher temperatures is more soluble. Other ways of obtaining supersaturated solutions are, for example, combining two solutions, the ingredients of which react to form another substance that does not immediately fail (prevented or delayed precipitation reactions). The latter mechanism is particularly suitable as the basis for the formation of matrices to be processed according to the invention.

In principle, the state of supersaturation can be achieved with any type of solution, although, as already mentioned, the principle described in the present application is preferably used in the production of detergents and cleaning agents. Accordingly, some systems that tend to form supersaturated solutions in principle are less suitable according to the invention, since the underlying substance systems cannot be used ecologically, toxicologically or for economic reasons. In addition to nonionic surfactants or common non-aqueous solvents, curing mechanisms are therefore particularly preferred according to the invention, in which a supersaturated aqueous solution is used as the basis for at least one matrix to be processed.

As already mentioned above, the state of supersaturation in the context of the present invention relates to the saturated solution at 20 ° C. By using solutions that have a temperature above 20 ° C, the state of supersaturation can easily be reached. Crystallization-hardening compositions according to the invention preferably have a temperature between 35 and 120 ° C., preferably between 40 and 110 ° C., particularly preferably between 45 and 90 ° C. and in particular between 50 and 80 ° C. during processing present invention preferred.

Since the detergent and cleaning agent portions produced are generally neither stored at elevated temperatures nor used later at these elevated temperatures, the cooling of the mixture leads to the precipitation of the proportion of solute from the supersaturated solution that exceeds the saturation limit at 20 ° C was included in the solution. The supersaturated solution can thus be divided into a saturated solution and a soil body when it cools down. However, it is also possible that recrystallization and hydration phenomena solidify the supersaturated solution to a solid upon cooling. This is the case, for example, when certain hydrated salts dissolve in their crystal water when heated. When cooling, supersaturated solutions are often formed here, which solidify through mechanical action or the addition of germs to a solid - the water containing salt as the state that is thermodynamically stable at room temperature. This phenomenon is known, for example, of sodium thiosulfate pentahydrate and sodium acetate trihydrate, with the latter salt containing hydrate in the form of the supersaturated solution being particularly useful in the process according to the invention. Also special washing and Detergent ingredients, such as phosphonates, show this phenomenon and, in the form of solutions, are ideal as granulation aids. For this purpose, the corresponding phosphonic acids (see below) are neutralized with concentrated alkali water, whereby the solution heats up due to the heat of neutralization. Upon cooling, solids of the corresponding alkali metal phosphonates are formed from these solutions. By incorporating further detergent and cleaning agent ingredients into the still warm solutions, matrices of different composition that can be processed according to the invention can be produced. It is particularly preferred that the supersaturated solution serving as the basis of the curing matrix solidifies to a solid at room temperature. It is preferred here that the previously supersaturated solution, after solidification to a solid by heating to the temperature at which the supersaturated solution was formed, cannot be converted back into a supersaturated solution. This is the case, for example, with the phosphonates mentioned.

The supersaturated solution serving as the basis of the hardening matrix can - as mentioned above - be obtained in several ways and then processed after optional addition of further ingredients. A simple way is, for example, that the supersaturated solution serving as the basis of the curing matrix is prepared by dissolving the solute in heated solvent. If higher amounts of the solute are dissolved in the heated solvent than would dissolve at 20 ° C, then there is a supersaturated solution in the sense of the present invention, which is either hot (see above) or cooled and in the metastable state in the Mixer can be given.

It is also possible to dehydrate salts containing hydrate water by "dry" heating and to dissolve them in your own water of crystallization (see above). This is also a method for producing supersaturated solutions which can be used in the context of the present invention.

Another way is to add a gas or another liquid or solution to a non-supersaturated solution so that the solute reacts in the solution to a poorly soluble substance or dissolves poorly in the mixture of solvents. Combining two solutions, each containing two substances that react with each other to form a poorly soluble substance, is also a method for producing supersaturated solutions, as long as the poorly soluble substance does not fail immediately. It is also preferred in the context of the present invention that the supersaturated solution serving as the basis of the hardening matrix is prepared by combining two or more solutions. Examples of such ways to make supersaturated solutions are discussed below.

It is preferred that the supersaturated aqueous solution, preferably by combining an aqueous solution of one or more acidic ingredients of detergents and cleaning agents the group of surfactant acids, builder acids and complexing agents, and an aqueous alkali solution, preferably an aqueous alkali hydroxide solution, in particular an aqueous sodium hydroxide solution.

Among the representatives of the compound classes mentioned above, the phosphonates in particular have an outstanding position in the context of the present invention. In preferred processes according to the invention, therefore, the supersaturated aqueous solution is combined by combining an aqueous phosphonic acid solution with concentrations above 45% by weight, preferably above 50% by weight and in particular above 55% by weight, based in each case on the phosphonic acid solution and an aqueous sodium hydroxide solution Concentrations above 35 wt .-%, preferably above 40 wt .-% and in particular above 45 wt .-%, each based on the sodium hydroxide solution.

According to the invention, the matrix can also be cured by chemical reaction (s), in particular polymerization. In principle, all chemical reactions are suitable which, starting from one or more liquid to pasty substances, lead to solids by reaction with (another) substance (s). Chemical reactions that do not suddenly lead to the state change mentioned are particularly suitable. From the variety of chemical reactions that lead to the solidification phenomenon, reactions are particularly suitable in which larger molecules are made up of smaller molecules. Again, this preferably includes reactions in which many small molecules react to (one) larger molecule (s). These are so-called polyreactions (polymerization, polyaddition, polycondensation) and polymer-analogous reactions. The corresponding polymers, polyadducts (polyaddition products) or polycondensates (polycondensation products) then give the shaped body which has been cut to length its strength.

With regard to the intended use of the products produced according to the invention, it is preferred to use the formation of such solid substances from liquid or pasty starting materials as the curing mechanism, which in the detergent and cleaning agent are anyway used as ingredients, for example cobuilders, soil repellents or soil release Polymers are to be used. Such cobuilders can originate, for example, from the groups of polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, etc. These classes of substances are described below.

Another mechanism by which the deformable composition (s) can be cured in the context of the present invention is that of the curing, which takes place by changing the rheological properties. This takes advantage of the property that certain substances can drastically change their rheological properties under the influence of shear forces. Examples of such systems which are known to the person skilled in the art are, for example, layered silicates which have a strong thickening effect under shear in suitable matrices and can lead to cut-resistant masses.

In summary, for reasons of technical feasibility, portion packs according to the invention are particularly preferably characterized in that the flowable material is a solidified melt.

In addition to a (possibly solidifying or hardening) liquid, the flowable material can also be particulate. Portion packagings according to the invention are preferred here, which are characterized in that the flowable material is a total of particles whose average particle size is below 1200 μm, preferably below 300 μm, particularly preferably below 250 μm and in particular below 200 μm.

Depending on the desired application, the portions according to the invention can contain different detergent or cleaning agent ingredients. The different areas such as core, individual core region (in the case of multi-phase cores), matrix or individual matrix region can be used to separate incompatible ingredients.

The most important ingredients that can be contained in the portions according to the invention are described below.

The detergent or cleaning agent portions according to the invention preferably contain surfactant (s), it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the detergent or cleaning agent portions is preferably below 30% by weight, based on the total agent. Nonionic surfactants have already been described above as optional plasticizers for the coating. The same substances can also be used in the portions as washing-active substances, so that reference can be made to the above statements. 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 ester.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-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 VIII below,

R '

R-CO-N- [Z] VIII

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 group of polyhydroxy fatty acid amides also includes compounds of the formula IX below, R ¹ -0-R ²

R-CO-N- [Z] IX

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.

[Zj is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The content of non-ionic surfactants in preferred detergent or cleaning agent portions according to the invention which are suitable for textile washing is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the total agent.

Low-foaming nonionic surfactants are preferably used in automatic dishwashing detergents.

Anionic, cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent. In contrast, these surfactants are of significantly greater importance in detergents. The detergent or cleaning agent portions according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.

The agents according to the invention can contain, for example, cationic compounds of the formulas X, XI or XII as cationic active substances: R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (X)

(CH ₂ ) _n -TR ²

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (XI)

R 'T T

RR ²

R ¹

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (XII)

R ⁴

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O- CO- or -CO-O- and n is an integer from 0 to 5.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as those obtained from C _12-18 monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are for example derived from C ₁₂ ι ₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. The esters are also the same of D-sulfo fatty acids (ester sulfonates), for example the D-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

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 sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₅ alkyl sulfates are preferred for washing technology reasons. 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 _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-1 alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι _2-18 - 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 _8-18 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). In turn, there are sulfosuccinates whose fatty alcohol residues differ from ethoxylated fatty alcohols with a narrow homolog distribution derive, particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alkyl (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow 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 anionic surfactant content of preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition. Cleaning agents according to the invention for machine dishwashing are preferably free from anionic surfactants.

In the context of the present invention, preferred agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and sliding agents and UV absorbers.

The builders that can be contained in the agents according to the invention include, in particular, phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

The use of the generally known phosphates as builder substances is possible according to the invention, 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), have 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 (HP0 ₃ ) _π and orthophosphoric acid H ₃ P0 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Sodium dihydrogenphosphate, NaH ₂ P0 ₄ , exists as a dihydrate (density 1, 91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^'3 ). Both salts are white powders which are very easily soluble in water Heat the crystal water and lose it at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0 ₇ ), at higher temperature into sodium trimetaphosphate (Na ₃ P ₃ 0 ₉ ) and Maddrell's salt (see below). NaH ₂ P0 ₄ reacts acidic; it forms when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed in. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ P0 is a white salt the density 2.33 like ^'3 , has a melting point of 253 ° [decomposes to form potassium polyphosphate (KP0 ₃ ), J and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0 ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly ^"3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 mol. Water ( Density 1, 52 like ^'3 , melting point 35 ° with loss of 5 H ₂ 0), becomes anhydrous at 100 ° and changes to diphosphate Na P ₂ 0 ₇ when heated more. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0 ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ P0 ₄ , are colorless crystals which, as 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 0 ₅ ) have a melting point of 100 ° C. and, in anhydrous form (corresponding to 39-40% P ₂ 0 ₅ ), a density of 2.536 ^{″ 3} . 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 P0 ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price in the detergent industry, the more soluble ones are therefore highly effective, potassium phosphates often preferred over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ 0 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 water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ 0 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), K ₄ P ₂ 0 ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33, preferably ³ , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ P0 ₄ or the KH ₂ P0 ₄ 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 O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n that crystallizes with 6 H ₂ 0 -Na with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 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 O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0). 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:

(NaP0 ₃ ) ₃ + 2 KOH - Na ₃ K ₂ P ₃ O ₁₀ + H _z O According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; 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 also be used according to the invention.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x + 1} ^' H ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. 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 disilicates Na ₂ Si ₂ 0 ₅ -yH ₂ 0 are preferred.

Amorphous sodium silicates with a Na ₂ 0: Si0 modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which delay the dissolution, can also be used are and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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 (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula nNa ₂ 0 ^• (1-n) K ₂ 0 ^■ Al ₂ 0 ₃ ^■ (2 - 2.5) Si0 ₂ ^■ (3.5 - 5.5) H ₂ 0

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Other important builders are in particular the carbonates, citrates and silicates. Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or metasilicates are preferably used.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances are considered to be alkali carriers, alkali metal carbonates, in particular sodium carbonate, in particular sodium bicarbonate or sodium sesquicarbonate being used for the purposes of this invention.

A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.

A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

In addition, other ingredients may be present, washing, rinsing or cleaning agents according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.

Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients. The solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. The anhydrides of these acids can also be used as acidifying agents, in particular maleic anhydride and succinic anhydride are commercially available. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.

Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1, 3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.

In the context of the present invention, particular preference is given to detergent or cleaning agent portions which contain one or more chelate complexing agents from the groups of

(i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, (ii) nitrogen-containing mono- or polycarboxylic acids,

(iii) geminal diphosphonic acids,

(iv) aminophosphonic acids,

(v) phosphonopolycarboxylic acids,

(vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the By means of, included.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:

a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 3-nitridodiacetic acid, nitridodiacetic acid , N-di- (β-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms and derivatives thereof containing hydroxyl or amino groups, and 1-aminoethane-1, 1-diphosphonic acid, their higher homologues with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methy lenphosphonic acid) or nitrilotri (methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred. Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.

Deposit-inhibiting polymers can also have cobuilder properties. Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. 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 action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of 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 or scale inhibitors; these are, 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.

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

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.

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 preferably have 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. Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

Further suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyolcarboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof 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 effect 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 syrups 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. 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. Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used 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 hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-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). As Aminoalkane phosphonates are preferably 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, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition to the substances from the classes of substances mentioned, the agents according to the invention can contain further usual ingredients of detergents, dishwashing detergents or cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ -supplying acid salts or peracids such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent tablets. 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. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned 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 phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, ethylene glycol, diacetoxy-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 Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

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 of 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. Oxireductases can also be used to bleach or inhibit the transfer of color. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. 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 especially 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 amylases, isoamylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-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 0.12 to about 2% by weight.

Detergent portions according to the invention for machine dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing. The known substances of the prior art can be used. Generally can especially silver protection agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.

In order to improve the aesthetic impression of the agents 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.

Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials. For inventive as a textile detergent Assembled suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic Cellulose ethers and the polymers of phthalic acid and / or terephthalic acid or 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 thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention made up as textile detergents in order to eliminate graying and yellowing of the treated textiles. These substances absorb onto the fiber and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible convert longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry. Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2 ^'- stilbenedisulfonic (flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles opti. brighteners are usually used in amounts of between 0.05 and 0.3% by weight, based on the finished composition.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the composition

The agents according to the invention can also be provided with further additional benefits. Here are, for example, agents made up according to the invention as textile detergents dye transfer inhibiting compositions, agents with "anti-gray formula", agents with ironing relief, agents with special fragrance release, agents with improved dirt release or prevention of re-soiling, antibacterial agents, UV protection agents, color refreshing agents, etc. can be formulated. Some examples are explained below :

Since textile fabrics, in particular made from rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending and kinking. If pressing and squeezing across the grain are sensitive, the agents according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkyl olesters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the agents according to the invention can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuriacetate, and these compounds can also be dispensed with entirely in the agents according to the invention.

Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines , Phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-dicyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above.

The antimicrobial agent can be selected from ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerin, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2.4 , 4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) - N- (3,4-dichlorophenyl) urea, N, N '- (1, 10-decanediyldi) 1-pyridinyl-4-ylidene) -bis- (1-octanamine) - dihydrochloride, N.N'-bis ^ -chlorpheny -S. ^ - diimino ^^. H .IS-tetraaza-tetradecanediimidamide, glucoprotamines, antimicrobial surface-active quaternaries Compounds, guanidines including the bi- and polyguanidines, such as, for example, 1,6-bis- (2-ethylhexyl-biguanido-hexane) dihydrochloride, 1.δ-DKN ^ N _T '-phenyldiguanido-Ns.Ns ^ hexane-tetrahydochloride, 1, 6-Di- (Nι, N ₁ '- phenyl-N _L N methyldiguanido-Ns.Ns'J-hexane-dihydrochloride, 1, 6-Di- (N. |, Nι'-o-chlorophenyldiguanido- N ₅ , N ₅ ') -hexane-dihydrochloride, l .δ-DN _L N-i' ^. Θ-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, 1, 6-di- [N ₁ , N ₁ ' -beta - (p-methoxyphenyl) diguanido-N ₅ , N ₅ '] -hexane-dihydrochloride, 1, 6-di- (N ₁ , N ₁ ' -alpha-methyl-.beta.-phenyldiguanido-N ₅ , N ₅ ' ) -hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ '-p-nitrophenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, omega: omega-di- (Nι, N-ι'- phenyldiguanido -N ₅ , N ₅ ') -di-n-propylether-dihydrochloride, omega: omega'-di- (N ₁ , Nι'-p-chlorophenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-tetrahydrochloride , 1, 6-Di- (N ₁ , N '-2,4-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, 1, 6-Di- (Nι, N ₁ '-p-methylphenyldiguanido-N ₅ , N ₅ ') hexane-dihy hydrochloride, l .θ-Di ^ Ni.N _ϊ '^ Aδ-trichlorophenyldiguanido-Ns.Ns'Jhexanetrahydrochloride, l .θ-DKN ^ Ni'-alpha-chlorophenyl) ethyldiguanido-N ₅ , N ₅ ' j hexane - dihydrochloride, omegaOmega-D Ni.N ^ -p-chlorophenyldiguanido-Ns.Ns'Jm-xylene-dihydrochloride, 1, 12-Di- (N ₁ , N ₁ '-p-chlorophenyldiguanido-N ₅ , N ₅ ') dodecane dihydrochloride, 1, 10-di- (Nι, Nι'- phenyldiguanido-N ₅ , N ₅ ') decane tetrahydrochloride, l N ₅ , N ₅ ') dodecane-tetrahydrochloride, 1, 6-di- (Nι, N ₁ ' -o-chlorophenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, 1, 6-di- (N ₁ , N ₁ '-o-chlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, ethylene bis (1-tolyl biguanide), ethylene bis (p-tolyl biguanide), ethylene bis (3,5-dimethylphenyl biguanide) ), Ethylene bis (p-tert-amylphenyl biguanide), ethylene bis (nonylphenyl biguanide), ethylene bis (phenyl biguanide), ethylene bis (N-butylphenyl biguanide), ethylene bis (2,5-diethoxyphenyl biguanide) , Ethylene bis (2,4-dimethylphenyl biguanide), ethylene bis (o-diphenyl biguanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene bis (phenyl biguanide), trimethylene bis (o-tolyl biguanide) , N-butyl-trimethyl-bis- (phenyl biguanide) and the corresponding salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocosalkyl sarcosinates, phosphites, hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates Maleate, Tartrate, Fumarate, Ethylene Miami ntetraacetates, iminodiacetates, cinnamates, thiocyanates, arginates, pyromellitates, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial active ingredients of vegetable origin (for example from spices or herbs), animal and microbial origin are also suitable. Preferably, antimicrobial surface-active quaternary compounds, a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline, and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, Sulfonium, phosphonium, iodonium or arsonium group, peroxo compounds and chlorine compounds can be used. Substances of microbial origin, so-called bacteriocins, can also be used.

The quaternary ammonium compounds (QAV) suitable as antimicrobial active ingredients have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^" , in which R ¹ to R ^{4 have the} same or different CC ₂₂ alkyl radicals , C ₇ -C ₂₈ aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and represent X-halide ions, sulfate ions, Hydroxide ions or similar anions For optimum antimicrobial activity, at least one of the radicals preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV are by reacting tertiary amines with alkylating agents such as Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAV are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzyl-ammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyl-dimethyl-C12-alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57 -09-0), benzetonium chloride (N, N-dimethyl-N- [2- [2- [p- (1, 1, 3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chloride such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3 ), Dioctyl-dimethyl-ammoniumchloric, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and their mixtures. Particularly preferred QAV are the benzalkonium chlorides with C ₈ -C ₁₈ -alkyl radicals, in particular C ₁₂ -C ₁₄ -alkyl-benzyl-dimethyl-ammonium chloride.

Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ^® ex Lonza, Marquat® ^® ex Mason, Variquat ^® ex Witco / Sherex and Hyamine ^® ex Lonza and as Bardac ^® ex Lonza. Other commercially available antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide ^® and Dowicil ^® ex Dow, Benzethonium chloride such as Hyamine ^® 1622 ex Rohm & Haas, methylbenzethonium chloride such as Hyamine ^® 10X ex Rohm & Haas, cetylpyridinium chloride such as cepacol chloride ex Merrell Labs.

The antimicrobial active ingredients are preferably used in amounts of from 0.0001% by weight to 1% by weight, preferably from 0.001% by weight to 0.8% by weight, particularly preferably from 0.005% by weight to 0.3 % By weight and in particular from 0.01 to 0.2% by weight.

In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antstatics, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional softening effect.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being able to be used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Links, which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are also suitable.

Another object of the present invention is a method for producing water-soluble portion packaging with at least one core therein and a matrix of flowable material at least partially surrounding the core (s), which comprises the steps a) production of a portion packaging which is open on one side from water-soluble Material; b) filling the portion packaging with one or more core (s) and fixing the core or cores; c) filling the portion packaging with the flowable matrix; d) sealing the portion packaging is marked.

The portion packaging, which is open on one side, can be produced by conventional methods of thermoforming polymers, deep-drawing, so-called rotary die processes, blow molding (blow extrusion) and injection molding being of particular importance. The following explanations focus on the particularly preferred production by injection molding processes, but also apply mutatis mutandis to the other thermoforming processes known from the prior art.

The one-sided open portion packs to be produced according to the invention can, for example, be blow molded, injection molded, thermoformed or calendered. Suitable blow molding processes include extrusion blow molding, coextrusion blow molding, injection stretch blow molding and immersion blowing. The injection molding is carried out according to methods known per se at high pressures and temperatures with the steps of closing the mold connected to the extruder for injection molding, injecting the polymer at high temperature and high pressure, cooling the injection-molded molding, opening the mold and removing the molded blank , Further optional steps such as the application of release agents, demolding etc. are known to the person skilled in the art and can be carried out using technology known per se. Preferred methods according to the invention are characterized in that the portion packaging which is open on one side is produced by injection molding or thermoforming, preferably deep drawing.

As explained in detail above, the core can be produced, for example, by tableting or casting, but it can also be a gelatin capsule or the like. his. Preferred methods according to the invention are characterized in that the core is produced by tableting.

With regard to the fixation of the core, reference can be made to the explanations above. Methods according to the invention are preferred here in which the core is fixed to the water-soluble sheathing by positioning the core in a shaped cavity of the sheathing. Also preferred are methods in which the core is fixed to the water-soluble sheath by positioning the core in one of the sheaths and subsequent shrinking back of the sheath material, and methods in which the core is fixed to the water-soluble sheath by an adhesive connection.

The sealing in step d) takes place, for example, by sealing with a thin, water-soluble film, by means of a “stopper” closing an opening, or in another conventional manner. Preferred methods according to the invention are characterized in that the filled packaging is sealed by sealing a film, the thickness of which is preferably 10 to 100 μm, particularly preferably 20 to 75 μm and in particular 30 to 50 μm.

Claims

claims:

1. portion packaging, comprising a water-soluble covering and at least one core therein and a matrix of flowable material at least partially surrounding the core (s), characterized in that the core (s) is / are fixed to the water-soluble covering ,

2. portion packaging according to claim 1, characterized in that the water-soluble envelope one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and their derivatives, in particular MC, HEG, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof.

3. portion packaging according to one of claims 1 or 2, characterized in that polyvinyl alcohols and / or PVAL copolymers, the degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and is in particular 82 to 88 mol%, polyvinyl alcohols and / or PVAL copolymers having a molecular weight in the range from 3,500 to 100,000 gmol ^"1 , preferably from 10,000 to 90,000 gmol ^{" 1} , particularly preferably from 12,000 to 80,000 gmol ^{'1 being} preferred and in particular from 13,000 to 70,000 gmol ^"1 and particularly preferred polyvinyl alcohols and / or PVAL copolymers have an average degree of polymerization between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio MG (50% ) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

4. portion packaging according to any one of claims 1 to 3, characterized in that the water-soluble envelope comprises hydroxypropylmethyl cellulose (HPMC) having a degree of substitution (average number of methoxy groups per anhydroglucose unit of cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.

5. portion packaging according to one of claims 1 to 4, characterized in that the water-soluble envelope is formed from a film material whose thickness is 10 to 1000 microns, preferably 20 to 750 microns and in particular 30 to 500 microns.

6. portion packaging according to one of claims 1 to 5, characterized in that the core is a tablet.

7. portion packaging according to one of claims 1 to 6, characterized in that the core is a solidified melt.

8. portion packaging according to one of claims 1 to 7, characterized in that the core is spatially delimited by an internal web or a weir.

9. portion packaging according to one of claims 1 to 8, characterized in that the core is fixed to the water-soluble envelope by positioning the core in a shaped cavity of the envelope.

10. portion packaging according to one of claims 1 to 9, characterized in that the core is fixed to the water-soluble casing by shrink-wrapping material.

11. portion packaging according to one of claims 1 to 9, characterized in that the core is fixed to the water-soluble envelope by an adhesive connection.

12. portion packaging according to one of claims 1 to 11, characterized in that the flowable material is a liquid whose viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ° C, spindle 3) preferably in the range of 500 to 50,000 mPas, more preferably from 1000 to 10,000 mPas, particularly preferably from 1200 to 5000 mPas and in particular from 1300 to 3000 mPas.

13. portion packaging according to one of claims 1 to 11, characterized in that the flowable material is a solidified melt.

14. Portion packaging according to one of claims 1 to 11, characterized in that the flowable material is a total of particles, the average particle size is below 1200 microns, preferably below 300 microns, particularly preferably below 250 microns and in particular below 200 microns.

15. A process for the production of water-soluble portion packaging with at least one core therein and a matrix of flowable material at least partially surrounding the core (s), characterized by the steps e) production of a portion packaging made of water-soluble material which is open on one side; f) filling the portion packaging with one or more core (s) and fixing the core or cores; g) filling the portion packaging with the flowable matrix; h) Close the portion packaging.

16. The method according to claim 15, characterized in that the portion packaging open on one side is produced by injection molding or thermoforming, preferably deep drawing.

17. The method according to any one of claims 15 or 16, characterized in that the core is produced by tableting.

18. The method according to any one of claims 15 to 17, characterized in that the core is fixed to the water-soluble sheathing by positioning the core in a shaped cavity of the sheathing.

19. The method according to any one of claims 15 to 17, characterized in that the core is fixed to the water-soluble sheathing by positioning the core in one of the sheathing and subsequent shrinking back of the sheathing material.

20. The method according to any one of claims 15 to 17, characterized in that the core is fixed to the water-soluble coating by an adhesive connection.

21. The method according to any one of claims 15 to 17, characterized in that the closed packaging is sealed by sealing a film, the thickness of which is preferably 10 to 100 μm, particularly preferably 20 to 75 μm and in particular 30 to 50 μm.