DE10223266C1 - Tablets with close-fitting water-soluble sheath, used in domestic washing machine and automatic dishwasher, especially in rinse-in compartment, contain swellable disintegration agent - Google Patents

Abstract

Tablets with a water-soluble sheath in close contact on the tablets contain swellable disintegration agent(s). Independent claims are also included for the following: 1. production of the tablets by (a) placing a water-soluble film on a molding tool, (b) placing the tablet(s) in the mold(s), (c) laying another film on the tablet(s) in the mold(s) and (d) sealing and optionally cutting the film; 2. production of the tablets by passing 2 films through a pair of contrarotating molding rollers with recesses, so that (a) the films are sealed at the edge of a recess by the rollers, (b) a tablet is placed between the 2 films, (c) the rollers take the film-covered tablet into a recess and coat it with the film, (d) the film-covered tablet is sealed to the other edge of the recess by the molding roller.

Description

The present invention is in the field of compact molded articles which are washable. and have cleaning-active properties. Such detergents and cleaning agents Shaped articles include, for example, detergent tablets for washing Textiles, detergent tablets for automatic dishwashing or Cleaning hard surfaces, bleach tablets for use in washing or Dishwashers, water softening tablets or stain remover tablets; this Individual offer forms are hereinafter referred to as "washing or Detergent tablets "summarized. In particular, the invention relates to Use of detergent tablets for washing textiles in a household washing machine (detergent tablets).

Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and to handle and because of their compact structure Advantages in storage and transport. Also in the Patent literature therefore includes detergent tablets described. A problem with the application of washing and cleaning active Moldings occur again and again, is the too slow disintegration and dissolution rate the molded body under conditions of use. Because sufficiently stable, d. H. Form and break-resistant molded articles produced only by relatively high compression pressures can, there is a strong compression of the molded parts and resulting in a delayed disintegration of the shaped body in the aqueous Brisk and thus too slow a release of the active substances in the washing or Cleaning process. The delayed disintegration of the moldings still has the Disadvantage that many detergent tablets do not have the  Have the detergent dispenser washed in by household washing machines as the tablets are not in decay into secondary particles sufficiently small time that are small enough to get out Detergent dispenser to be washed into the washing drum. Another problem that occurs especially with detergent tablets, the friability of Moldings or their often insufficient stability against abrasion. So you can sufficiently break-stable, d. H. hard detergent tablets made often, however, these are the burdens of packaging, transport and handling, d. H. Falling and rubbing stresses, not sufficiently grown so that edge breakage and signs of abrasion impair or even impair the appearance of the molded body lead to a complete destruction of the molded structure.

To overcome the dichotomy between hardness, i.e. H. Transport and handling Stability and easy disintegration of the moldings are many in the prior art Approaches have been developed. A well known and in particular from the pharmacy the area of detergent tablets is a broad approach Incorporation of certain disintegration aids that facilitate access to water or swell upon entry of water or gas evolving or in another form act disintegrating. Other proposed solutions from the patent literature describe the Compression of premixes of certain particle sizes, the separation of individual ones Ingredients of certain other ingredients as well as the coating of individual Ingredients or the entire molded body with binders.

A disadvantage of the detergent tablets on the market is that they still have to be provided with an outer packaging that contains the ingredients Protects environmental influences (especially moisture). These "flow packs" out Water-insoluble materials must be removed by the consumer before dosing what can be annoying to the consumer and causes waste. Approaches to solutions This problem is the coating of the molded body with water-soluble polymers or the use of water-soluble packaging.

A coating provides visually appealing tablets with a smooth, shiny surface Surface and advantageous, haptic properties. However, the coating of tablets technically complex and expensive. The use of water-soluble packaging  is described in the form of bags of water-soluble film in the prior art. However, tablets packed in this way can no longer be dosed via the dispenser, since the water-soluble material prevents water from entering the tablet and thus the Disintegration of the molded body prevented for too long, so that the flushing process is ended and the tablet remains undissolved in the induction chamber or at least larger ones Residues caused.

The European patent EP 888 448 B1 discloses a cleaning agent concentrate for the Production of ready-to-use aqueous cleaning agent solutions in cleaning agents storage tanks of cleaning machines, in particular high-pressure cleaners, spray Extraction equipment or the like, which gas-splitting in contact with water Component comprises, the detergent concentrate in portions in a water-soluble wrapping is packaged in such a way that the wrapping on the Detergent concentrate is in close contact, but the coating of a coating applied to the detergent concentrate is different. The gas-releasing shower system causes that once the inside of the enclosure any detergent concentrate in contact with water, d. H. in education the first leak in the envelope, gas is released, which is the envelope inflates and finally blows up and the detergent concentrate completely surrounding water. The increased gas development that occurs leads to a stirring effect that dissolves the water-soluble coating, but also the other Components of the concentrate, greatly accelerated. According to the teaching of this scripture at least 20 wt .-% shower system can be used to achieve acceptable dissolution times to arrive in the minute range. These periods are for a wash-in Detergent dispenser way too long.

DE 199 49 981 A1 discloses detergent tablets which are in one Tubular bags made of water-soluble film are packed.

The present invention was based on the object of using aesthetically to enable appealing detergent or cleaning agent tablets that are not compatible with a Outer packaging must be provided from water-insoluble film and still over the Detergent dispenser of household washing machines are disposable. The tablets should  in contrast to tablets in tubular bags made of water-soluble film be flushable without residue.  

It has now been found that an envelope made of water-soluble film, which is close to the Shaped body is present, a Einspülbarkeit via the induction chamber allows when the Tablets at the same time a swellable disintegration aid in granular, contain cogranulated or compacted form.

The subject of the present invention is in a first embodiment Use of detergent tablets made of compressed, particulate Detergent comprising a water-soluble coating which is so that the middle one is in close contact with the detergent tablet Distance between detergent tablet and water-soluble coating over the entire Area of the detergent tablet is 0.1 to 1000 microns, the tablet at least one swellable disintegration aid based on cellulose in granular, cogranulated or compacted form and the tablet free of gas-evolving effervescent systems is, as detergent tablets for household washing machines.

In the simplest case, a cellulose-containing material or pure cellulose can pass through Granulation, compacting or other application of pressure in secondary particles are transferred, which swell on contact with water and thus serve as an explosive. As a cellulosic material, wood pulp has proven itself, which can be achieved by thermal or chemical-thermal processes from wood or wood chips (sawdust, sawmill waste) is accessible. This cellulose material from the TMP process (thermo mechanical pulp) or the CTMP (chemo-thermo mechanical pulp) process can then be carried out Application of pressure compiled, preferably roller compacted and in Particle shape can be transferred. Of course, pure analogue can also be used Use cellulose, which is more expensive in terms of raw materials. Here both microcrystalline as well as amorphous, finely divided cellulose and mixtures thereof be used.  

Another way is to add the cellulosic material Granulating aids to granulate. As pelletizers, for example Solutions of synthetic polymers or non-ionic surfactants have proven their worth.

In order to avoid residues on the washed textiles, the primary fiber length should the cellulose used or the cellulose in the cellulose-containing material is less than 200 μm lie, with primary fiber lengths below 100 microns, especially below 50 microns are preferred. The secondary particles ideally have a particle size distribution, in which more than 90% by weight of the particles have sizes above 200 µm. Someone specific Dust content can improve the storage stability of the tablets produced with it contribute. Fractions of a fine dust fraction of less than 0.1 mm up to 10% by weight, preferably up to 8% by weight can be used in the invention Disintegrant granules are present.

The finely divided cellulose preferably has bulk densities of 40 g / l to 300 g / l, entirely particularly preferably from 65 g / l to 170 g / l. Are already granulated types used, their bulk density is higher and can be in an advantageous embodiment 350 g / l to 550 g / l. The bulk weights of the cellulose derivatives are typically in the Range from 50 g / l to 1000 g / l, preferably in the range from 100 g / l and 800 g / l.

As already stated, cellulose-based disintegration aids can also be used use which contain other active ingredients or auxiliaries besides cellulose. Are suitable here, for example, compacted disintegrant granules from 60-99% by weight of non-water soluble, water-swellable cellulose and optionally other modified water-swellable polysaccharide derivatives, 1-40% by weight of at least one polymer Binder in the form of a polymer or copolymer of (meth) acrylic acid and / or their salts, and 0-7% by weight of at least one liquid, with water gel-forming surfactants. These disintegrants preferably have a moisture content from 2 to 8% by weight.

The proportion of cellulose in such disintegrant granules is between 60 to 99% by weight, preferably between 60 to 95% by weight. These explosives can also be used Use regenerated celluloses like viscose. Particularly regenerated celluloses in  Powder form is characterized by very good water absorption. The viscose powder can be made from cut viscose fiber or by precipitating the dissolved viscose getting produced. Low molecular weight cellulose is also degraded by electron beam suitable for example for the production of such disintegrant granules.

Furthermore, those contained in the detergent tablets according to the invention swellable disintegration aid in water swellable cellulose derivatives, such as Cellulose ethers and cellulose esters and starch or starch derivatives and other swellable Polysaccharides and polygalactomannans contain, for example ionically modified Celluloses and starches such as carboxymethyl-modified cellulose (CMC) and starch, nonionically modified celluloses and starches, such as alkoxylated celluloses and starches, such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl (HPC) and Hydroxyethyl cellulose (HEC) and alkyl etherified products such as methyl cellulose (MC) and mixed modified celluloses and starches from the aforementioned Modifications, if necessary combined with a modification, for networking leads. Suitable starches are also cold-swelling starches, which can be produced by mechanical or degrading reactions are formed on the starch grain. These include above all Swelling starches from extruder and drum dryer processes as well as enzymatic, oxidizing or acid-degrading modified products. Contain chemically derivatized starches preferably substituents by sufficient ester and ether groups the polysaccharide chains are attached.

Starches with ionic substituents such as carboxylate, hydroxyalkyl or Phosphate groups have been modified, have proven to be particularly advantageous and are therefore preferred. The use has also been used to improve the swelling behavior proven by slightly cross-linked strengths. Alkaline-treated starches can also be used their good cold water swellability can be used. In an advantageous Embodiment has been the combination of cellulose with cellulose derivatives and / or Starch and / or starch derivatives proven. The proportions can vary widely Boundaries fluctuate; based on the combination, the proportion of cellulose derivatives is and / or starch and / or starch derivatives preferably 0.1 to 85% by weight, particularly preferably 5 to 50% by weight.  

Polymers are used as binders in preferred disintegration aid granules or copolymers of (meth) acrylic acid or mixtures of such polymers or Copolymers used. The polymers are selected from the group Homopolymers of (meth) acrylic acid, from the group of copolymers with the following Monomer components of ethylenically unsaturated dicarboxylic acids and / or their Anhydrides and / or ethylenically unsaturated sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or Crosslinkers and / or graft bases based on polyhydroxy compounds.

Uncrosslinked polymers or copolymers of (Meth) acrylic acid, with weight average molecular weights of 5,000 to 70,000 proved. The copolymers are preferably copolymers of (Meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, for example 40 to 90% by weight Contain (meth) acrylic acid and 60 to 10% by weight of maleic acid or maleic anhydride, their relative molar mass, based on free acids, between 3,000 and 100,000, is preferably 3,000 to 70,000 and very particularly preferably 5,000 to 50,000. As Well-suited binders have also been found in ter- and quattropolymeric polycarboxylates proven, built up from (meth) acrylic acid, maleic acid and optionally fully or partially saponified vinyl alcohol derivatives, or those from (meth) acrylic acid, ethylenically unsaturated sulfonic acids and polyhydroxy units such as sugar derivatives, or those from (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and sulfonic acid groups containing monomers.

The polymeric binders are preferably used in the form of their aqueous form Solutions used, but can also be used in the form of fine powder. The binder polymers are preferably in partially or fully neutralized form, the salt formation preferably with cations of alkali metals, ammonia and Amines, or their mixtures.

The proportion of polymers / copolymers in preferred disintegrants is between 1 and 40% by weight, preferably between 1 and 20% by weight, particularly preferably between 5 and 15% by weight. Polymer contents above 15% in the disintegrant lead to harder ones  Disintegrant granules, while polymer contents below 1% to form soft granules tend to be less abrasion resistant.

Suitable polymer binders are also crosslinked polymers made from (meth) acrylic acid. she are preferably used as finely divided powders and preferably have medium ones Particle sizes from 0.045 mm to 0.150 mm and are preferably 0.1 to 10% by weight used. Particles with average particle sizes above 0.150 mm do indeed result also good disintegrant granules, but lead after the dissolving with the granules tablets produced to visually visible as particle swelling bodies, which For example, in the case of textile washes, clearly visible on the textile in disruptive Deposit way. The combination represents a special embodiment of the invention of soluble poly (meth) acrylate homo- and copolymers and the aforementioned finely divided crosslinked polymer particles.

Disintegrant granules used preferably contain or as a further component several liquid, gel-forming surfactants selected from the group of nonionic, anionic or amphoteric surfactants, which are used in amounts up to 7% by weight, preferably up to 3.5 wt .-% can be present. If the surfactant content in the Disintegrant is too high, in addition to increased abrasion of the manufactured with it Tablets also have poor swelling properties.

The nonionic surfactants are described in detail below.

Disintegration aids preferably used according to the invention are notable for a special swelling kinetics, the expansion depending on the time does not change linearly, but reaches a very high level after a very short time. The swelling behavior in the first 10 seconds after is of particular interest Contact with water. The specific water absorption capacity is preferably used Disintegration aid can be determined gravimetrically and is preferably 500 to 2000%.  

Fluid intake (also known as specific porosity) is more preferred Disintegrant is in a range of over 600 ml / kg, preferably over 750 ml / kg, especially in the range of 800 to 1000 ml / kg.

Granulated disintegrant granules are first produced by mixing the Granulate components with usual mixing processes. For example, the mixer Companies Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. at In this first step of mixing and granulating, pre-compounds are processed Agglomeration process produced.

In the next step, these pre-compounds are mechanically compressed. The condensing using pressure can be done in several ways. The products can between two pressure surfaces in roller compressors, e.g. B. smooth or profiled, compressed become. The compactate is ejected as a strand. Compression methods in Matrices with stamps or cushion rollers produce compact forms, such as tablets or Briquettes. As compacting machines, roller compactors, extruders, roller or cube presses, but also pelletizing presses.

Compression with pelleting presses has proven to be particularly suitable by means of a suitable process control, granules which are obtained without further Shredding can be dried. Suitable pelleting presses are e.g. B. from the Manufactured by Amandus Kahl and Fitzpatrick.

The coarse, compacted particles are crushed, z. B. mills, shredders or Roller mills are suitable. The shredding can be done before or after drying be performed. Preferred water contents of 2-8% by weight, preferably 2.5-7% by weight and particularly preferably 3-5% by weight become. For this, conventional dryers, such as. B. drum dryer (temperatures e.g. from 95-120 ° C) or fluid bed dryer (temperatures e.g. from 70-100 ° C).

Coprocessates which are suitable as swellable disintegration aids are also suitable can be obtained from polysaccharide material and insoluble disintegrants. As Polysaccharide materials are the substances from the groups mentioned above  powdered cellulose, microcrystalline cellulose and mixtures thereof in particular suitable; as an insoluble disintegrant there are particularly insoluble ones Polyacrylic acid monopolymer, insoluble polyacrylamide monopolymer, insoluble polyacrylic acid-polyacrylamide copolymer and mixtures thereof in Consideration.

The content of the individual components in these explosives can continue within Limits vary, for example from 1 to 60% by weight of insoluble polyacrylic product. Disintegrant and 40 to 99% by weight cellulose. A content of 3 to 60% by weight is preferred. insoluble polyacrylic product disintegrant and 40 to 97 wt .-% cellulose. A content of 5 to 30% by weight of insoluble polyacrylic product is even more preferred. Disintegrant and 70 to 95 wt .-% cellulose. You can optionally use this explosive small amounts of other disintegrants, for example various starches, Shower mixes e.g. B. from sodium carbonate and sodium bisulfate, etc. added be, these amounts by appropriate deductions from the amount of cellulose balanced d. H. be compensated.

This suitable disintegrant can be coprocessed as defined above Cellulose with an insoluble disintegrant as defined above by moist or dry compression can be obtained under pressure. Under the term "coprocessing" is a dry compression z. B. between opposing compacting rollers Press 20-60 kN, preferably 30-50 kN, or wet compacting Addition of water, by kneading or pressing moist plastic masses through a Sieve, a perforated disc or via an extruder and then drying Roger that.

In summary, a use according to the invention in which the tablet is preferred the swellable disintegration aid based on cellulose in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 1 to 8% by weight and in particular from 2 to 7% by weight, based in each case on the Molded body weight, contains.  

The coated detergent tablets used according to the invention have a Wrapping made of water-soluble material. This can be a single material or one Blend different materials. In preferred uses according to the invention the water-soluble envelope comprises one or more materials from the group Polyvinyl alcohol (PVAL), acetalized polyvinyl alcohol and / or PVAL copolymers, Polyvinyl pyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and their Derivatives, especially MC (methyl cellulose), HEC (hydroxyethyl cellulose), HPC (Hydroxypropyl cellulose), HPMC (hydroxypropyl methyl cellulose) and / or CMC (Carboxymethyl cellulose), and / or copolymers and mixtures thereof. Possibly. can the envelopes plasticizers known to those skilled in the art to increase flexibility of the material.

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

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

contain.

Commercially available polyvinyl alcohols with white-yellowish powder or granules Degree of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered, have degrees of hydrolysis of 98-99 or 87-89 mol%, contain a residual content of acetyl groups. The poly are characterized Manufacturers of vinyl alcohols by specifying the degree of polymerization of the product initial polymers, the degree of hydrolysis, the saponification number or the solution viscosity.  

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and few strong polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They do not become from (chlorinated) hydrocarbons, esters, fats and oils attacked. Polyvinyl alcohols are classified as toxicologically harmless and are biodegradable at least partially. The water solubility can be checked Aftertreatment with aldehydes (acetalization), by complexing with Ni or Cu Reduce 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, however, allows water vapor to pass through.

Preferred uses in the context of the present invention are thereby characterized in that the water-soluble coating polyvinyl alcohols and / or PVAL Includes copolymers whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, is particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used, with preferred uses according to the invention in which the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers, the molecular weight in the range from 3,500 to 100,000 gmol ^-1 , preferably from 10,000 to 90,000 gmol ^-1 , particularly is preferably 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 about 2100, preferably between about 220 to about 1890, especially preferably between about 240 to about 1680 and especially between about 260 to about 1500.

Preferred uses according to the invention are characterized in that the comprises water-soluble coating polyvinyl alcohols and / or PVAL copolymers, the 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%) between 0.3 and 1, is 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 trademark Mowiol® (Clariant). As part of the present Polyvinyl alcohols particularly suitable according to the invention 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 a 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 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 K.K.). 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):

by the radical polymerization of 1-vinylpyrrolidone by the process of or suspension polymerization using radical formers (peroxides, azo Compounds) are prepared as initiators. The ionic polymerization of the Monomers only delivers products with low molecular weights. commercial Polyvinylpyrrolidones have molar masses in the range of approx. 2500-750000 g / mol which are about the specification of the K values are characterized and - depending on the K value - Have glass transition temperatures of 130-175 °. They are considered white, hygroscopic Powder or offered as aqueous solutions. Polyvinylpyrrolidones are readily soluble in Water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, Chlorinated hydrocarbons, phenols and the like a.).

Copolymers of vinyl pyrrolidone with other monomers are also suitable, especially vinyl pyrrolidone / vinyl ester copolymers, such as those under the Trademark Luviskol® (BASF) are sold. Luviskol® VA 64 and Luviskol® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred, nonionic polymers.

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

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

The vinyl esters are polymerized by free radicals using various processes (Solution polymerization, suspension polymerization, emulsion polymerization, Bulk polymerization.). Contain copolymers of vinyl acetate with vinyl pyrrolidone Monomer units of the formulas (I) and (II).

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

H- (O-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) mostly in the presence of small amounts of water. You have depending Reaction control molar masses in the range of approx. 200-5,000,000 g / mol, accordingly Degree of polymerization from approx. 5 to <100,000.

The products with molar masses <approx. 25,000 g / mol are liquid and at room temperature are referred to as the actual polyethylene glycols, abbreviation PEG. This Short chain PEGs can in particular other water-soluble polymers, e.g. B. 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 considered 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 this is preferably used together with other polymers. Gelatin is one Polypeptide (molecular weight: approx. 15,000 to <250,000 g / mol), mainly by hydrolysis  of the collagen contained in the skin and bones of animals under acidic or alkaline Conditions is won. The amino acid composition of the gelatin corresponds largely that of the collagen from which it was obtained and varies depending on of its provenance. The use of gelatin as a water-soluble shell material is extremely wide, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules common. Gelatin is found in the form of foils because of its compared to the above mentioned polymers high price only little use.

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 methyl hydroxypropyl cellulose, as are sold, for example, under the trademarks 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 manufactured industrially by etherification of alkali cellulose (e.g. with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying 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 uses according to the invention are characterized in that the water-soluble coating hydroxypropylmethyl cellulose (HPMC) which comprises 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, having.

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 SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - COO ^- - or -SO ₃ ^- contain groups, and summarized such polymers that contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer which can be used according to the invention is the acrylic resin available under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, Methacrylic acid and 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 other ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the prior art cited therein. 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 under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL) available octylacryl amide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-Hydroxypropylmethacrylat- Copolymers.

Water-soluble, anionic polymers suitable according to the invention include:

• - Vinyl acetate / crotonic acid copolymers, 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)
• - Vinylpyrrolidone / vinyl acrylate copolymers, available for example under the Trademark Luviflex® (BASF). A preferred polymer is under Name Luviflex® VBM-35 (BASF) available vinyl pyrrolidone / acrylate Terpolymers.
• - Acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers, 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 are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid, those which are used with low molecular weight aliphatic alcohols, in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-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:
  are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie 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:
  • a) at least one monomer of the non-ionic type,
  • b) at least one monomer of the ionic type,
  • c) of polyethylene glycol and
  • d) a crosslinker
  The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.
  The nonionic monomers can be of very different types and the following are preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.
  The nonionic 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:
  • 1. 5 to 85% by weight of at least one monomer of the nonionic type,
  • 2. 3 to 80% by weight of at least one monomer of the ionic type,
  • 3. 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
  • 4. 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).
• - Copolymers obtained by copolymerizing at least one monomer from each of the following three groups:
  • 1. esters of unsaturated alcohols and short-chain, saturated carboxylic acids and / or esters of short-chain, saturated alcohols and unsaturated carboxylic acids,
  • 2. unsaturated carboxylic acids,
  • 3. 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 _3-18 alcohol
• - Among short-chain carboxylic acids or alcohols are those with 1 to 8 To understand carbon atoms, the carbon chains of these compounds optionally interrupted by double-bonded hetero groups such as -O-, -NH-, -S- could be.
• - 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 of one or more allyl or methallyesters of the formula VII:
  wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated, straight-chain or branched C _1-6 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% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% allyl or methallyl radicals of the formula VII.
• - Tetra and pentapolymers made of:
  • 1. Crotonic acid or allyloxyacetic acid
  • 2. Vinyl acetate or vinyl propionate
  • 3. branched allyl or methallyl esters
  • 4. Vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters
• - Crotonic acid copolymers with one or more monomers from the group Ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
• Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated, aliphatic monocarboxylic acid branched in the α-position.

Other polymers which can preferably be used according to the invention as a coating are cationic Polymers. The cationic polymers include the permanently cationic ones Polymers preferred. According to the invention, such are considered to be “permanently cationic” Designates polymers that have a cationic group regardless of the pH. These are usually polymers that have a quaternary nitrogen atom, for example in the form an ammonium group.

Preferred cationic polymers are, for example:

• - Quaternized cellulose derivatives, such as those under the names Celquat® and Polymer JR® are commercially available. The connections Celquat® H 100, Celquat® L 200 and Polymer JR®400 are preferred, quaternized cellulose derivatives vate.
• - Polysiloxanes with quaternary groups, such as those obtained commercially products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning® 929 emulsion (containing a hydroxylamino modified silicone, also called amodimethicone), SM-2059  (Manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, Quaternium-80),
• - Cationic guar derivatives, in particular those under the trade names Products distributed by Cosmedia® Guar and Jaguar®,
• - Polymer Dimethyldiallylammoniumsalze and their copolymers with esters and Amides of acrylic acid and methacrylic acid. The under the designations Mer quat®100 (poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyl diallylammonium chloride-acrylamide copolymer) commercially available products are examples of such cationic polymers.
• - Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, such as vinyl quaternized with diethyl sulfate pyrrolidone-dimethylaminoethyl methacrylate copolymers. Such connections are under the names Gafquat®734 and Gafquat®755 are commercially available.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers, as described under the Be drawing Luviquat®.
• - quaternized polyvinyl alcohol

as well as those under the designations:

• - polyquaternium 2,
• - polyquaternium 17,
• - Polyquaternium 18 and
• - Polyquaternium 27

known polymers with quaternary nitrogen atoms in the main polymer 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.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives as well as polymeric dimethyldiallylammonium salts and their copolymers. cationic Cellulose derivatives, especially the commercial product Polymer®JR 400, are complete particularly preferred, cationic polymers.  

The casing of the detergent tablets used according to the invention can be used in addition to the water-soluble polymer or the water-soluble polymers further ingredients contain, which in particular the processability of the starting materials Improve serving. Plasticizers and release agents are particularly worth mentioning here. In addition, dyes and / or fragrances and optical brighteners can in the water-soluble coating are incorporated in order to achieve aesthetic effects there.

According to the invention, in particular hydrophilic, high-boiling substances can be used as plasticizers Use liquids, where appropriate also as solid at room temperature Solution, dispersion or melt can be used. Particularly preferred Plasticizers come from the group glycol, di, tri, tetra, penta-, hexa-, hepta-, Octa-, Nona-, Deca-, Undeca-, Dodecaethylenglycol, Glycerin, Neopentylglycol, Trimethylolpropane, pentaerythritol, mono-, di-, triglycerides, surfactants, in particular Nonionic surfactants and their mixtures.

Ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, strong hygroscopic liquid which is miscible with water, alcohols and acetone and a Density of 1.113. The freezing point of ethylene glycol is -11.5 ° C, the Liquid boils at 198 ° C. Technically, ethylene glycol is made from ethylene oxide Heating with water obtained under pressure. Promising manufacturing processes leave also on the acetoxylation of ethylene and subsequent hydrolysis or on Build synthesis gas reactions.

Diethylene glycol (2,2'-oxydiethanol, digol), HO- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -OH, is a colorless, viscous, hygroscopic, sweet-tasting liquid, density 1.12, which is -6 ° C melts and boils at 245 ° C. Diglycol is miscible in any ratio with water, alcohols, glycol ethers, 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 WO ₃ contact via the glycide stage.

Trimethylolpropane [TMP, Etriol, Ettriol, 1,1,1-Tris (hydroxymethyl) propane] is chemical exactly called 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, however insoluble in aliphatic and aromatic hydrocarbons. The production takes place by reaction of 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, a melting point of 262 ° C. as well has 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 (cerotinic 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 glycerol here are, in particular, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% C _14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _C18 ', 1 wt .-% C ₁₈ "), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt _10% C, 50 wt .-% _C12, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _C18 ', 1 wt .-% C ₁₈ "), tallow fatty acid (approx. 3% by weight C ₁₄ , 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 wt% C ₁₇ , 63 wt% C ₁₈ , 1 wt% C ₁₈ '), technical oleic acid (approx. 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 wt .-% C _18', 10 wt .-% C ₁₈ ", 0 , 5 wt% C ₁₈ '''), technical palmitic / stearic acid (approx. 1 wt% C ₁₂ , 2 wt% C ₁₄ , 45 wt% C ₁₆ , 2 wt% C ₁₇ , 47 wt .-% C ₁₈ , 1 wt .-% C ₁₈ ') and soybean oil oleic acid (approx. 2 wt% C ₁₄ , 15 wt% C ₁₆ , 5 wt% C ₁₈ , 25 wt% C ₁₈ ', 45 wt% C ₁₈ ", 7 wt% 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. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 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 _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

It is particularly preferred to use nonionic surfactants as plasticizers which have a melting point above room temperature. As a result, are preferred Envelopes characterized in that non-ionic surfactant (s) are used as plasticizers 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 43.3 ° C, used become.

Suitable, nonionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming, nonionic Surfactants that can be solid or highly viscous at room temperature. Become at Room temperature highly viscous nonionic surfactants used, it is preferred that this one Viscosity above 20 Pa.s, preferably above 35 Pa.s and in particular have above 40 Pa.s. Also nonionic surfactants, which are waxy at room temperature Have consistency are preferred.

Preferred nonionic surfactants to be used as solid at room temperature originate from the Groups of alkoxylated nonionic surfactants, especially ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as Polyoxypropylene / Polyoxyethylene / Polyoxypropylene (PO / EO / PO) surfactants.  

In a preferred embodiment of the present invention, this is nonionic Surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 C- 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 emerged.

A particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide won. Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, is / are preferred in particular, uses of the invention ethoxylated (s) nonionic surfactant (s) employed, the / from C _6-20 monohydroxyalkanols or C _{6- 20} -alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

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

Further nonionic surfactants to be used with particular preference, with melting points above Room temperature contain 40 to 70% of one Polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blends containing 75% by weight an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles  Ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles Ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Further preferred nonionic surfactants satisfy the formula:

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) 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 is at least 15.

Further nonionic surfactants which can preferably be used are the end-capped poly (oxyalkylated) nonionic surfactants of the formula:

R ¹ O [CH ₂ CH (R ³ ) O] _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, iso-propyl, n -Butyl, 2-butyl or 2-methyl-2-butyl, 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 group-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is:

R ¹ O [CH ₂ CH (R ³ ) O] _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, Be 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 converted under pressure in the presence of catalysts with CO ₂ to form glycerol carbonate. Glycerol carbonate is a clear, easily movable liquid with a density of 1.398 gcm ^-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 of density 1.0597, which solidifies at -32 ° C and boils at 214 ° C.  

1,3-propanediol can be prepared from acrolein and water, followed by catalytic hydrogenation.

Technically much more important is 1,2-propanediol (propylene glycol), which is an oily, colored loose, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and at Boiling at 188 ° C. 1,2-propanediol is made from propylene oxide by adding water.

Propylene carbonate is a bright, easily moving liquid with a density of 1.21 gcm ^-3 , the melting point is -49 ° C, the boiling point is 242 ° C. Large quantities of propylene carbonate can also be obtained by reacting propylene oxide and CO ₂ at 200 ° C and 80 bar.

As additional additives, which are preferably in solid form at room temperature, highly disperse silicas are particularly suitable. Here are pyrogenic Silicas such as the commercially available Aerosil® or precipitated silicas. Especially Preferred methods according to the invention are characterized in that as further Additives one or more materials from the group (preferably highly disperse) Silicic acid, 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 will become.

The water-soluble coatings can in turn contain disintegrants that accelerate the disintegration of the film by its swelling. Furthermore, these can Substances have a "wicking function" that prevents the wrapping from penetrating the Accelerated contact with water and thus the swelling of the contained in the tablet swellable disintegrant.

The water-soluble covering can be made of the materials mentioned above or their Mixtures can be obtained by injection molding or blow molding. The pouring can be either from the melt or from a solution with subsequent Drying done. There are also other methods for shaping plastics processing  suitable. For reasons of process economy, however, it is preferred that the water-soluble coating of the detergent tablets used according to the invention a film material is formed whose thickness is 10 to 100 microns, preferably 20 to 75 microns and in particular 30 to 50 microns.

The casing is in close contact with the detergent tablet, with the However, the cover is different from a coating applied to the tablet. The content of the tablet in swellable disintegration aid leads to the fact that, as soon as the detergent tablet inside the casing in contact with water arrives, d. H. when the first leak is formed in the casing or when it is exposed Moisturization, the tablet expands, the casing being blown up and the tablet is completely exposed to the surrounding water. This is the effect quickly that the subsequent flushing is not hindered by the flushing chamber, which enables residue-free flushing.

For the use according to the invention, it is important that the covering at every point the tablets are close to their surface. Ideally, the wrapping even stands under tension, but this is not absolutely necessary. This dense concern of. Coating is conducive to decay: the first time it comes into contact with water, the Allow the envelope to pass a small amount of water at some point, does not need to be solved at first. At this point it starts in the tablet to disintegrate contained explosives. This leads to the fact that the wrapping is now due to the The volume of the tablet suddenly tears open and the tablet releases. At a If the wrapping is not tight, the mechanism described here does not work because the tablet can swell without the casing being blown up. Here is the Use of a swellable disintegrant in a gas-developing system consider, because its explosive effect in any case to tear open the Wrapping leads. In a gas-generating system, the explosive effect can be caused by The gas escapes from a leak in the casing.  

Preferred uses according to the invention are characterized in that the Distance between detergent tablet and water-soluble coating over the entire Area of the detergent tablet 0.5 to 500 microns, preferably 1 to 250 microns and in particular 2.5 to 100 microns.

In a preferred embodiment, the film wrapping is first loosely around one Tablet placed and sealed and then shrunk onto the tablet so that a close contact between the foil packaging and the detergent concentrate given is. Accordingly, uses according to the invention are characterized in that that the wrapper is shrink-wrapped on the detergent tablet is.

The detergent tablets used according to the invention can be swellable Disintegration aid all other usual components of washing or Contain cleaning agents, which are briefly described below. It is also possible, so-called shower systems in the used according to the invention Incorporate detergent tablets; but it has been shown that these systems have a rather disruptive effect on the washability and little for the reason described above are effective so that the tablets used according to the invention are free of are gas-developing shower systems.

The detergent tablets used according to the invention preferably contain Surfactant (s), being anionic, nonionic, cationic and / or amphoteric surfactants can be used. Are preferred from an application technology perspective Textile detergents Mixtures of anionic and nonionic surfactants, the The proportion of anionic surfactants should be greater than the proportion of nonionic Surfactants. The total surfactant content of the detergent tablets is preferably below of 30 wt .-%, based on the total agent. Nonionic surfactants became more common already described above as an optional plasticizer for the wrapper. the same Substances can also be used as washing-active substances in the tablets.  

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R is a primary, straight-chain or methyl-branched, in particular methyl-branched, aliphatic radical with 8 to 22.1 preferably 12 to 18 C- Atoms means 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 preferred non-ionic surfactants, which either as sole, nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl ester.

Also 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 be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

Other suitable surfactants are polyhydroxy fatty acid amides of the following formula VIII:

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ 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 following formula 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] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propxylated derivatives of this residue.

[Z] 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 reacted with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

The content of preferred, more suitable for textile washing, usable according to the invention Detergent tablets of nonionic surfactants is 5 to 20% by weight, preferably 7 up to 15 wt .-% and in particular 9 to 14 wt .-%, each based on the total Medium.  

In combination with the surfactants mentioned, anionic, cationic and / or amphoteric surfactants are used. The used according to the invention Detergent tablets can therefore also be anionic, cationic as a surfactant component and / or contain amphoteric surfactants.

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

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 are obtained, for example, from C _12-18 monoolefins having a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Capron acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil 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 similar to that of the adequate compounds based on oleochemical raw materials. From the washing, the C ₁₂ are - C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates of preferably. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

Also 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 _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _12-18 -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, viewed in isolation, are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated and unsaturated fatty acid soaps, 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. B. 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 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, especially in the form of the sodium salts.

The anionic content of preferred textile detergents used according to the invention Surfactants is 5 to 25 wt .-%, preferably 7 to 22 wt .-% and in particular 10 to 20 wt .-%, each based on the total agent.

Agents used in the context of the present invention additionally contain one or more substances from the group of builders, bleaches, Bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, Fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial Active substances, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, Ironing aids, phobing and impregnating agents, swelling and anti-slip agents as well as UV Absorber.

As builders, which can be contained in the agents used according to the invention, are in particular phosphates, silicates, aluminum silicates (in particular zeolites), Carbonates, salts of organic di- and polycarboxylic acids as well as mixtures of these substances to call. The use of the generally known phosphates as builder substances is possible according to the invention, provided that such use is not for ecological reasons should be avoided. Have among the variety of commercially available phosphates the alkali metal phosphates with particular preference for pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and Detergent industry the most important.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble, crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5H ₂ O) and 12 mol. Water (density 1.52 gcm ^-3 , melting point 35 ° with loss of 5H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. 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 HPO ₄ is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-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 triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate) Na ₄ P ₂ O ₇ exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 °, or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating 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 O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4. Condensation of the NaH ₂ PO ₄ or the KH ₂ PO 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 names 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 6H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n - Na with n = 3. In 100 g of water about 17 g of the salt of water free of water of crystallization dissolve at room temperature, about 20 g at 60 ° and about 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% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O.

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

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for 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 O ₅ .yH ₂ O are preferred.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving 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 / compaction 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) ), developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and by the formula:

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

can be described. 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 ₁₂ -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 are preferred Sodium carbonate and / or sodium bicarbonate and / or gluconate and / or silicate  Builder from the class of disilicate and / or metasilicate used.

Alkali carriers can be present as further constituents. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the the aforementioned substances, in the context of this invention preferably the alkali metal carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate be used.

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

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

In addition, other ingredients may be present, with those used according to the invention Detergents are preferred which additionally contain one or more substances from the group of Acidifying agents, chelating agents or the deposit-inhibiting polymers contain.

Both inorganic acids and organic acids can be used as acidifiers Acids, provided they are compatible with the other ingredients. For the sake of Consumer protection and handling safety are in particular the fixed mono-, Oligo- and polycarboxylic acids can be used. Again preferred from this group 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. Commercially available and as Acidifying agents are also preferred in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture of succinic acid, can be used (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances that form cyclic compounds with metal ions, where a single ligand has more than one coordination site on a central atom  busy, d. H. is at least "bidentate". In this case, normally elongated connections to form rings by complex formation via an ion 51992 00070 552 001000280000000200012000285915188100040 0002010223266 00004 51873. Die The number of ligands bound depends on the coordination number of the central ion.

Common and preferred in the context of the present invention Chelate complex images are, for example, polyoxycarboxylic acids, polyamines, Ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Also complex-forming polymers, i.e. polymers that are either in the main chain itself or laterally contribute to this functional groups that can act as ligands and with suitable metal atoms, usually with the formation of chelate complexes react, can be used according to the invention. The polymer-bound ligands of the emerging metal complexes can originate from only one macromolecule or but belong to different polymer chains. The latter leads to the networking of the Materials, provided that the complex-forming polymers have not previously been covalent Bonds were networked.

Complexing groups (ligands) of conventional, complex-forming polymers are iminodi acetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, Hydroxamic acid, amidoxime acid, aminophosphoric acid acid, (cycl.) Polyamino, mercapto, 1,3- Dicarbonyl and crown ether residues with z. T. very specific Activities towards ions different metals. Base polymers of many are also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, Polyvinyl alcohols, polyvinyl pyridines and polyethylene imines. Even natural polymers, such as cellulose, starch or chitin, are complex-forming polymers. In addition, you can this through polymer-analogous conversions with additional ligand functionalities be provided.

In the context of the present invention, particular preference is given to the use of detergent tablets which contain one or more chelating agents from the groups of:

• a) polycarboxylic acids in which the sum of the carboxyl and optionally Hydroxyl groups is at least 5,  
• b) nitrogen-containing mono- or polycarboxylic acids,
• c) geminal diphosphonic acids,
• d) aminophosphonic acids,
• e) phosphonopolycarboxylic acids,
• f) 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 agent.

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 like gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediamine triacetic acid, Diethy lentriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3- propionic acid, isoserine diacetic acid, N, 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 homologs with up to 8 carbon atoms and hydroxy or Derivatives thereof containing amino groups and 1-aminoethane-1,1-diphosphonic acid, their higher homologs with up to 8 carbon atoms and hydroxy or Derivatives thereof containing amino groups,
• d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylene triamine penta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid),
• e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and
• f) cyclodextrins.

As polycarboxylic acids a), carboxylic acids are included in this patent application Monocarboxylic acids - understood, in which the sum of carboxylic and those in the molecule contained hydroxyl groups is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, especially EDTA, are preferred. Both Alkaline pH values of the treatment solutions required according to the invention these complex bilgeers at least partially as anions. It is immaterial whether they are in Form of the acids or in the form of salts. In case of use as Salts are alkali, ammonium or alkylammonium salts, especially sodium salts, prefers.

Deposit-inhibiting polymers can also be used in the agents according to the invention be included. 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, with polymers with molecular weights below 15,000 daltons are preferred.

Deposit-inhibiting polymers can also have cobuilder properties. As Organic cobuilders can in particular be polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances will described below.

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

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

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 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 molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

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

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

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As Copolymers of acrylic acid with maleic acid have proven to be particularly suitable Contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular mass, based on free acids, is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar Derivatives included. Other preferred copolymers are those used as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate exhibit.

Likewise, as further preferred builder substances, polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, in addition to cobuilder properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained 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 obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme  lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which have a DE of 100 owns. Both maltodextrins with a DE between 3 and 20 can be used 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.

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 are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine N, N'-disuccinate (EDDS) preferably in the form of its sodium or magnesium salts used. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates. Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form can be present and which have at least 4 carbon atoms and at least one Contain hydroxy 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 is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate  (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta and octa Sodium salt of DTPMP, used. As a builder, the class becomes the Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it can, in particular if the agents also contain bleach, aminoalkanephosphonates are preferred, use in particular DTPMP, or mixtures of the phosphonates mentioned use.

In addition to the substances from the substance classes mentioned, they can be used according to the invention used agents contain other common ingredients of detergents, wherein in particular bleach, bleach activators, enzymes, silver preservatives, color and Fragrances are important. These substances are described below.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing, peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

To improve when washing at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be used in the washing and Detergent tablets are incorporated. Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result can be used. Are suitable Substances containing O and / or N-acyl groups with the number of carbon atoms mentioned and / or against also carry substituted benzoyl groups. Multiple acylates are preferred Alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides,  especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5- dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the moldings. With these Fabrics are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo Salene complexes or carbonyl complexes. Also 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 be used as bleaching catalysts.

Enzymes in particular come from the hydrolase classes, such as Proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases contribute to the removal of stains, such as protein, greasy or starchy stains and graying. Cellulases and others Glycosyl hydrolases can also be removed by removing pilling and Microfibrils help maintain color and increase the softness of the textile. Oxireductases can also be used to bleach or inhibit color transfer be used. Bacterial strains or fungi such as are particularly suitable Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens obtained enzymatic active ingredients. Proteases of the subtilisin type are preferred and in particular proteases derived from Bacillus lentus are used. there are enzyme mixtures, for example of protease and amylase or protease and Lipase or lipolytic enzymes or protease and cellulase or from Cellulase and lipase or lipolytically active enzymes or from protease, amylase and Lipase or lipolytic enzymes or protease, lipase or lipolytic acting enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular Interest. Examples of such lipolytically active enzymes are the known ones  Cutinases. Peroxidases or oxidases have also been found to be suitable in some cases proved. Suitable amylases include in particular α-amylases, iso-amylases, Pullulanases and pectinases. Cellobiohydrolases are preferably used as cellulases, Endoglucanases and β-glucosidases, which are also called cellobiases, or Mixtures of these are used. Because different types of cellulase are characterized by their CMCase and Avicelase activities can be distinguished by targeted mixtures of the Cellulases the desired activities can be set.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.12 to be about 2% by weight.  

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 adjust the pH of the agents used according to the invention to the desired range bring, the use of pH adjusting agents may be appropriate. Can be used here all known acids or bases, provided that their use is not apparent application-related or ecological reasons or for reasons of Prohibits consumer protection. The amount of these adjusting agents usually exceeds 5% by weight. not the overall wording.

In order to improve the aesthetic impression of the agents used according to the invention, they can be colored with suitable dyes. Preferred dyes whose Choices of no difficulty for the expert have a high Storage stability and insensitivity to the other ingredients of the agent and against light as well as no pronounced substantivity towards textile fibers to stain.

As foam inhibitors which are used in the agents used according to the invention can, for example, soaps, paraffins or silicone oils are considered can optionally be applied to carrier materials. suitable Antiredeposition agents, which are also referred to as soil repellents, are for example nonionic cellulose ethers, such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxy groups of 15 to 30 wt .-% and of hydroxypropyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether and on polymers of phthalic acid and / or terephthalic acid known in the prior art or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated derivatives are particularly preferred of the phthalic and terephthalic acid polymers.  

Optical brighteners (so-called "whiteners") can be used according to the invention Agents are added to prevent graying and yellowing of the treated textiles to eliminate. These substances absorb on the fiber and cause a lightening and feigning bleaching effect by turning invisible ultraviolet radiation into visible convert longer-wave light, which is absorbed from sunlight, ultraviolet Light is emitted as a weak bluish fluorescence and with the yellow tone of the greyed or yellowed laundry produces pure white. Suitable compounds are derived for example from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids (Flavonic acids), 4,4'-distyryl-biphenylene, methylumbelliferone, coumarins, Dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, Benzisoxazole and benzimidazole systems and those substituted by heterocycles Pyrene derivatives. The optical brighteners are usually used in amounts between 0.05 and 0.3 wt .-%, based on the finished agent used.

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. 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. Also water-soluble, acidic Group-containing polyamides are suitable for this purpose. Furthermore, use soluble starch preparations and starch products other than the above, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (Na salt) are preferred, Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methylhydroxypropylcellulose, methylcarboxymethylcellulose and their mixtures in Amounts of 0.1 to 5 wt .-%, based on the agent used

The agents used according to the invention can also be provided with additional benefits. For example, color transfer inhibiting compositions, agents with an "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 rayon, rayon, cotton and their blends, can tend to crease because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the fiber direction, the agents used 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, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

The agents used according to the invention can be used to control microorganisms contain antimicrobial agents. A distinction is made here depending on the antimicrobial Spectrum and mechanism of action between bacteriostatics and bactericides, Fungistatics and fungicides etc. Important substances from these groups are for example Benzalkonium chlorides, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, these compounds also being dispensed with entirely in the agents according to the invention can be.

To unwanted, caused by oxygen and other oxidative processes Prevent changes to the agents and / or the treated textiles which contain antioxidants. This connection class includes, for example substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

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

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate ironing of the treated textiles silicone derivatives, for example, are used in the agents used according to the invention become. 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 are one to have five carbon atoms and are partially or completely fluorinated. Preferred silicones are Polydimethylsiloxanes, which can optionally be derivatized and then are amino-functional or quaternized or Si-OH, Si-H and / or Si-Cl bonds exhibit. The viscosities of the preferred silicones are around 25 ° C between 100 and 100,000 centistokes, the silicones in amounts between 0.2 and 5% by weight, based on the total agent can be used.

Finally, the agents used according to the invention can also contain UV absorbers, which attach to the treated textiles and the lightfastness of the fibers improve. Compounds that have these desired properties are exemplary as the compounds and derivatives of the effective by radiationless deactivation Benzophenones with substituents in the 2- and / or 4-position. Furthermore, too substituted benzotriazoles, 3-phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid.

The coated detergent tablets used according to the invention stand out Compared to conventional detergent tablets by a number of advantages: You have an aesthetic appearance, have advantages in handling (convenience), because no waste has to be disposed of during use; they avoid contact of the Consumers to the active ingredients when touching the tablet have high mechanical Stability and have no abrasion and no crumbs.  

To produce the coated detergent tablets used according to the invention detergent tablets are first produced in a manner known per se. This Tablets are first made by dry blending the ingredients can be fully or partially pre-granulated, and then provide information, in particular pressing into tablets, using conventional methods can be used. To make the tablets, the premix is in a So-called die between two stamps compressed into a solid compressed. This process, which is briefly referred to below as tableting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and expelling.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body by the position of the lower one Stamp and the shape of the press tool can be determined. The constant one Dosage even at high molding throughputs is preferably over a volumetric dosage of the premix reached. In the further course of tableting the upper stamp touches the premix and continues to lower towards the Lower stamp. With this compression, the particles of the premix become closer pressed together, the void volume within the filling between the Stamping decreases continuously. From a certain position of the upper stamp (and the plastic begins at a certain pressure on the premix Deformation in which the particles flow together and it to form the molded body comes. Depending on the physical properties of the premix, a part also becomes the premixed particles are crushed, and there is a pressure at even higher pressures Sintering the premix. With increasing press speed, i.e. high Throughput quantities, the phase of elastic deformation is shortened more and more, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is made using the lower stamp pressed out of the die and by subsequent transport devices carried away. At this point, only the weight of the molded body is final  determined because the compacts due to physical processes (stretching, crystallographic effects, cooling etc.) can still change their shape and size.

Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only the Upper stamp used to build up pressure, the lower stamp also moves during of the pressing process towards the upper punch, while the upper punch presses down. Eccentric tablet presses are preferably used for small production quantities, where the stamp or stamps are attached to an eccentric disc, which in turn an axis with a certain rotational speed is mounted. The movement this ram is comparable to the way a conventional four-stroke engine works. The pressing can be done with an upper and lower stamp; but it can also several stamps can be attached to an eccentric disc, the number of Die holes are expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, on which one so-called die table a larger number of dies is arranged in a circle. The number of matrices varies between 6 and 55, depending on the model, with larger ones as well Matrices are commercially available. Each die on the die table is a top and Assigned lower stamp, whereby again the pressure is active only by the upper or Lower stamp, but can also be built up by both stamps. The matrix table and the stamps move about a common, vertical axis, the Stamp with the help of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and discharge. To the Places where there is a particularly serious increase or decrease in the stamp is necessary (filling, compacting, ejecting), these cam tracks are additional low-pressure pieces, low-tension rails and lifting tracks supported. The The die is filled via a rigidly arranged feed device so-called filling shoe, which is connected to a storage container for the premix. The pressure on the premix is via the press paths for upper and lower punches individually adjustable, the pressure build-up by rolling the Stamp shaft heads happen on adjustable pressure rollers.  

Rotary presses can also be used with two filling shoes to increase the throughput be provided, with only a semicircle to produce a tablet must become. Several are used to produce two- and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. Appropriate process management is based on this Way to produce coated and dot tablets that have an onion skin-like Have structure, whereby in the case of the point tablets the top of the core or Core layers are not covered and thus remain visible. Also Rotary tablet presses can be equipped with single or multiple tools, so that for example, an outer circle with 50 and an inner circle with 35 holes can be used for pressing at the same time. The throughputs are more modern Rotary tablet presses are over a million tablets per hour.

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

• - Use of plastic inserts with small thickness tolerances
• - Low number of revolutions of the rotor
• - Big filling shoes
• - Matching the filler paddle speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed

All of the technology is available to reduce the build-up of stamps known non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps also turned out to be proven to be advantageous, the upper and lower punches being rotatable if possible should be. With rotating stamps, a plastic insert can usually be used to be dispensed with. The stamp surfaces should be electropolished here.  

It was also shown that long pressing times are advantageous. You can use Pressure rails, several pressure rollers or low rotor speeds can be set. Because the fluctuations in hardness of the tablet due to the fluctuations in the pressing forces systems should be used that limit the pressing force. Here can elastic stamps, pneumatic compensators or spring elements in the Kraftweg be used. The pressure roller can also be designed to be resilient.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V .; Halle (BE / LU) as well Mediopharm Kamnik (SI). For example, the hydraulic one is particularly suitable Double printing press HPF 630 from LAEIS, D. are tabletting tools for example from Adams Tablettierwerkzeuge, Dresden; Wilhelm Fett GmbH, Schwarzenbek; Klaus Hammer, Solingen; Herber & Söhne GmbH, Hamburg; Hofer GmbH, Weil; Horn & Noack, Pharmatechnik GmbH, Worms; Ritter Pharmatechnik GmbH, Hamburg; Romaco, GmbH, Worms, and Notter Werkzeugbau, Tamm available. Other providers are e.g. B. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can be in a predetermined spatial shape and a predetermined size are manufactured. Practically all sensibly manageable come as a room shape Configurations into consideration, for example, the training as a board, the staff or Bar shape, cubes, cuboids and corresponding room elements with flat side surfaces as well as in particular cylindrical configurations with circular or oval Cross-section. This last embodiment covers the form of presentation from the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.  

The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Tablets without dosing aid can be dosed directly into the induction chamber where they are dissolve during the induction process.

But it is also possible that the various components do not become one Tablet are pressed, but that shaped bodies are obtained, which several Have layers, that is, at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous, application-related properties of the shaped bodies result. If, for example, components are contained in the moldings, the affect each other negatively, so it is possible to have one component in the faster integrate soluble layer and the other component into a slower soluble Work in layer so that the first component has already reacted when the second goes into solution. The layer structure of the moldings can be stacked, a dissolution process of the inner layer (s) at the edges of the molded body already then occurs when the outer layers have not yet been completely dissolved; but it can also a complete encapsulation of the inner layer (s) by the further outside lying layer (s) can be reached, which prevents the early Solution of components of the inner layer (s) leads.

In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Moldings, the outermost layers, however, are free of peroxy bleach. Farther it is also possible to use peroxy bleaching agents and any bleach activators present and / or spatially separate enzymes from each other in a molded body.  

In addition to the layer structure, multiphase moldings can also be in the form of Ring-core tablets, core-coated tablets or so-called "bulleye" tablets are produced become. An overview of such embodiments of multi-phase tablets is in the EP 055 100 (Jeyes Group). This document discloses toilet cleaners Blocks a molded body from a slow-dissolving cleanser comprise composition in which a bleach tablet is embedded. This font at the same time reveals the most diverse forms of design in a multi-phase manner Shaped bodies from simple multi-phase tablets to complicated, multilayer systems with deposits.

After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to:

Here σ stands for diametral fracture stress (DFS) in Pa; P is the force in N, which leads to the pressure exerted on the molded body, which Causes breakage of the molded body; D is the shaped body diameter in meters, and t is the Height of the molded body.

The wrapping of the tablets with a tight-fitting wrapper has the other Advantage that the pressures can be reduced. Because of the tight wrapping the stability of the tablets is significantly improved: tablet breakage and edge breakage prevented; the friability (tendency to wear) is reduced to zero. This increased stability enables packaging in bulk in a secondary pack, for example one Carton. Since the tight wrapping makes the tablet mechanically more stable, the Hardness of the tablet can be reduced. This can save explosives, the Formula can thus be made more compact.  

After the tablets have been produced, they are converted into forms which are the Can take tablets. The molding tools can be used as individual units be designed; however, it is also possible and for reasons of process economy preferred to use molds that have a variety of shapes. about These shapes are placed on a water-soluble film, which is subsequently inserted the tablet (s) is pressed into the mold (s).

Alternatively, the film can be supported before inserting the tablet Heating and / or vacuum can be inserted into the mold. Here are preferred Process characterized in that the deformation of the water-soluble film by inserting the tablet (s) in step b) by heating the film and / or applying a vacuum is supported.

The height of the shape determines the position of the sealing seam created later. In one The second step is the foil-lined or covered form with a tablet filled. A second sheet of the film is placed over the form filled with the tablet and then stretched with a sealing tool and with the lower film sealed together.

If the tablet inserted into the mold is flush with the top of the mold, the sealing seam is created as a "brim" on a string surface of the tablet. Here you can go to Sealing a simple plate can be used, but has the disadvantage that the film covering the top of the tablet is also exposed to heat.  

Alternatively, you can also design the sealing seam so that it on the outer surface of the Tablet runs along. In this case, the tablet is out of shape and over the part of the tablet protruding from the mold is covered with another film. Sealing cannot now be done with a plate-like sealing tool, but is done with an annular tool. This method has the advantage that the lowering of the ring-shaped sealing tool also tightens the upper film. In addition, the heat effect on the tablet is clear compared to a "heating plate" reduced.

In summary, methods are preferred in which the tablet (s) in step b) follow the insertion into the mold (s) does not end flush with the top of the mold, but protrudes / protrudes from it, whereby in preferred processes the seal with an annular sealing tool (s) takes place, the opening area (s) has / have ways through which the tablet fits.

The term "ring-shaped sealing tool" does not refer to circular "rings" in the narrow sense. Rather, this term also includes rectangular or square, oval, triangular or other, also completely irregular shapes. The annular sealing tool only needs to be the shape of the tablets to be sealed be adapted so that it can be put over the tablet. Ideally, that's it over the entire surface of the tablet close to the surface.

In this process variant, it is aesthetically disadvantageous that the sealing seam protrudes. First, it is detrimental to the aesthetic appearance of the product; on the other hand could suggest to the consumer that the wrapper before the application of the Product would have to be removed. This can be done through a further process step can be eliminated by using an annular sealing tool on the outer surface the tablet is placed and sealed.

Therefore, another embodiment does not contain a protruding sealing seam. This will either placed on the lateral surface so that it is not or only barely recognizable, or  a method of inserting the tablet into the wrapper is used that does not protruding sealing seam can be seen.

Another process variant for the production of envelopes with little or no Recognizable seam therefore provides for the sealed seam to be sealed to the Seal the surface of the tablet. This is the preferred method characterized in that the tablet (s) in step b) after insertion into the mold (s) seals / closes flush with the top of the form, with the tablet during Sealing step d) is raised, whereby the sealing seam on the outer surface of the tablet is sealed.

Here the top film, which is on the form in which the bottom film and tablet are located, with a ring-shaped sealing tool, the inside of which is at sealing temperature brought on, pressed on top of the mold, the tablet will come out of the mold pushed out through the sealing tool, with the sealing tool on the outside the surface of the tablet is pressed and the top and bottom film together welded. This creates a barely visible seam.

A further process variant provides that the tablets are either processed according to the methods disclosed above or according to conventional packaging methods of the prior art the technology in water-soluble films and then the film packaging shrink on the molded body. This shrink film is a film that has been stretched and contracts again when heated. Here it is possible to work very closely with the Generate wrappings on the surface of the tablet.

Likewise preferred methods are characterized in that as water-soluble Foil (s) used in steps a) and c) are pre-stretched foils, which in step d) or subsequently shrunk onto the tablet (s).

Another method for tightly wrapping tablets with water-soluble film consists in using form rollers which have depressions into which the Fit the tablets. The use of form rollers enables several Process variants. For one, tablets can be made from a water-soluble tape  Foil stored and transported, covered with another, water-soluble film and sealed at a certain point in the apparatus with a sealing form roller become. As an alternative, the second, water-soluble film can also only be close to the sealing form roller are fed.

A reverse process variant is to put a water-soluble film on a Applying the form roller, feeding tablets to the film-covered molds and on one seal the water-soluble film supplied to another place.

The methods described above use a form roller in conjunction with a plane. Advantageously, however, two counter-rotating form rollers can also be used, the forms ideally being able to hold half a tablet each. A process carried out in this way for the production with water-soluble coatings of tightly coated detergent tablets is characterized in that two foils made of water-soluble material are passed through a pair of opposing shaping rollers which have depressions, wherein:

• a) the films are sealed together by the forming rollers at the edge of a depression become;
• b) a tablet is placed between the two foils sealed together;
• c) the rollers take the film-covered tablet in a recess while doing so cover with the film;
• d) the film-covered tablet on the other edge of the depression through the shaping roller is sealed.

This method enables the production of large quantities according to the invention usable detergent tablets.

Examples

A film of hydroxypropyl methyl cellulose was produced in the following way:

• - Prepare an 8% solution of MHPC 25 (Hercules) with 30% (based on MHPC) PEG 400 as a plasticizer.
• - Squeegee with a 400 µm squeegee
• - drying at 50 ° C
• - detachment from the substrate

The result was a transparent, glossy film with a thickness of 30 µm.

This film was used in the following examples to wrap Detergent tablets used.

example 1

The film obtained by the method described above was over a mold placed and into the mold with a commercially available Persil® detergent tablet pushed. The form filled with the film and the tablet was filled with another identically composed film covered and the films using an annular Sealing tool that seals only at the edges, heating the film-covered Avoids the tablet, welds it tightly to the tablet.

Analogously, commercially available Persil® tabs were provided with closely fitting films of the following types using the process described above:

• - Synthana PT 40, PT 30
• - Hydrolene (Idroplast) LFT 30, LFT 25, LFT 40

The following are the disintegration times of these tablets with and without wrapping certainly. For this purpose, the disintegration times of 2 similar tablets were determined Immersion in water determined using a stopwatch. The decay times at Immersion in water was between 10 and 20 s for the uncoated tabs. The  Disintegration times of the coated tabs were between 15 s and 30 s. It can be seen that the Disintegration times can only be extended by 5-10 s due to the foils.

For comparison

A tablet packed in a tubular bag of the same film, needs a time of more than 1 min to disintegrate, what a dosage over the Detergent dispenser is too long.

The tablets described were placed in the induction drawer of a commercially available one Washer given (Miele W 918) and a normal washing program started. All tablets washed in without residue.

Furthermore, the diametrical fracture hardness of the coated and non-coated ones Tablets determined with a tablet hardness measuring device from Schleuniger. There were the hardness of the uncoated tablets at approx. 40 N; through the wrapping the Fracture hardness of the molded body can be increased to 120 N.

Claims (10)

1. Use of detergent tablets made of compressed, particulate detergent comprising a water soluble Envelope, which is in close contact with the detergent tablet that the mean distance between the detergent tablet and water-soluble Coating over the entire area of the detergent tablet is 0.1 to 1000 μm, wherein the tablet has at least one swellable disintegration aid Contains cellulose base in granular, cogranulated or compacted form and the The tablet is free of gas-evolving effervescent systems and can be dispensed into the dispenser Detergent tablets for household washing machines. 2. Use according to claim 1, characterized in that the tablet is the swellable Disintegration aid based on cellulose in granular, co-granulated or compacted form in amounts of 0.5 to 10% by weight, preferably 1 to 8% by weight and in particular from 2 to 7% by weight, based in each case on the molding weight, contains. 3. Use according to one of claims 1 or 2, characterized in that the water-soluble coating one or more materials from the group polyvinyl alcohol (PVAL), acetalized polyvinyl alcohol 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. 4. Use according to one of claims 1 to 3, characterized in that the comprises water-soluble coating polyvinyl alcohols and / or PVAL copolymers, the Degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferred 81 to 89 mol% and in particular 82 to 88 mol%. 5. Use according to one of claims 1 to 4, characterized in that the comprises water-soluble coating polyvinyl alcohols and / or PVAL copolymers, the Molecular weight in the range from 3,500 to 100,000 g / mol, preferably from 10,000 to 90,000 g / mol, particularly preferably 12,000 to 80,000 g / mol and in particular of 13,000 is up to 70,000 g / mol. 6. Use according to any one of claims 1 to 5, characterized in that the comprises water-soluble coating polyvinyl alcohols and / or PVAL copolymers, the 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%) between 0.3 and 1, preferably is between 0.4 and 0.8 and in particular between 0.45 and 0.6. 7. Use according to one of claims 1 to 6, characterized in that the water-soluble coating hydroxypropylmethyl cellulose (HPMC), which includes 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 having. 8. Use according to one of claims 1 to 7, characterized in that the water-soluble envelope is formed from a film material, the thickness of 10 to 100 microns, preferably 20 to 75 microns and in particular 30 to 50 microns. 9. Use according to one of claims 1 to 8, characterized in that the average distance between the detergent tablet and the water-soluble coating over the total area of the detergent tablet 0.5 to 500 microns, preferably 1 to 250 microns and is in particular 2.5 to 100 microns. 10. Use according to one of claims 1 to 9, characterized in that the Wrapping is a film packaging shrunk onto the detergent tablet.