DE10149719A1 - Production of flexible water-soluble hollow molding with compartment(s) filled e.g. with (laundry) detergent or conditioner, e.g. for use in washing machine or dishwasher, involves making parison, blow molding, filling and sealing - Google Patents

Abstract

Production of a flexible, preferably elastic, water-soluble hollow molding containing an agent, especially a laundry or other detergent or conditioner, comprises making a parison from a blow molding composition based on a water-soluble thermoplastic polymer, blow molding this to a hollow molding, filling the molding with agent(s) and providing a liquid-tight seal. Production of a flexible, preferably elastic, water-soluble hollow molding containing an agent (I), especially a laundry or other detergent or conditioner, comprises making a parison from a blow molding composition based on a water-soluble thermoplastic polymer, blow molding this to a hollow molding, filling the molding with (I) and providing a liquid-tight seal. The blow molding, filled with (I) or glycerol or unfilled, comprises: (1) a yield stress of 3-15 N/mm<2> in tension along its longest axis; (2) resilience of 0.05-5 Nm, in the direction of its shortest axis on vertical compression of 22 mm vertically, in the middle; (3) can be distorted by a force F1 of over 0.1 N and up to 500 N along a path s1 and returns in the direction of its original shape after the force is removed; (4) a recovery rate v of over 0.01 and up to 650 mm/minute after removing a distorting force; (5) an elastic modulus of <= 1, preferably <= 0.1, especially <= 0.01 GNm<2> for the wall of the flexible molding, when unfilled or \- 80 vol.% filled with (I); and/or (6) a compression resistance Fmax of 20-2000 N for the blow molding \- 80 vol.% filled with (I). Independent claims are included for the following: (1) Hollow moldings containing (I); and (2) Hollow moldings made by this process.

Description

The present invention relates to a method for producing a flexible, preferably elastic, water-soluble hollow body containing an agent, in particular a washing, care and / or cleaning agent, with at least one Compartment and a compartment hollow body and its use. Further The invention relates to washing, cleaning and care processes in which the detergent, Detergent and care product preparations in flexible, preferably elastic, Hollow bodies are dosed.

The state of the art describes extensively that detergents, cleaning agents or care products have so far usually been spray-dried or granulated solid products or as liquid goods. the Consumer's desire for convenient dosage options In addition to the two classic variants mentioned, products are pre-portioned Form established on the market and are also extensive in the prior art described. There are descriptions of detergents, cleaning agents or care products in the form of compressed molded articles, that is to say tablets, blocks, briquettes, rings and the like as well as portions of solid and / or liquid washing, packed in plastic bags Cleaning or care products.

In the case of single-dose amounts of detergents or cleaning agents contained in plastic bags packed into the market, there are foil bags made of water-soluble foil enforced. These make the packaging tear open by the consumer unnecessary. In this way it is easy to dispense a single portion or cleaning cycle by inserting the bag directly into the portion or cleaning cycle by inserting the bag directly into the Washing machine or dishwasher, especially in their dispenser, or by throwing the bag into a certain amount of water, for example in one Bucket, a bowl or in the hand wash or sink, possible. The washing, Foil bags surrounding detergent or care agent portion dissolves Reaching a certain temperature without residue. Also in bags Detergents and cleaning agents packaged in water-soluble film are state of the art described in large numbers. For example, the older patent application DE 198 31 703 discloses one portioned detergent or cleaning agent preparation in a bag water-soluble film, especially in a bag made of (optionally acetalized) Polyvinyl alcohol (PVAL), in which at least 70% by weight of the particles of the washing or Detergent preparation have particle sizes> 800 µm. such Foil bags or "pouches" are very consumer-friendly and make it easier Dosing, however, is not the most suitable form for dosing in all cases Detergent, cleaning agent and care product preparations, especially if Solid and liquid washing, cleaning or maintenance-active preparations side by side are dosing. Such bags also allow the incorporation of inelastic or volatile phases of detergents, cleaning agents or care products Do not add preparations to the detergent, cleaning agent or care agent portion. The pouches have in particular the disadvantage that the foil bags are opposite mechanical influences are quite sensitive. When transporting or Handling it can result in unwanted product leakage if the film is injured by carelessness. Simply touching with pointed or cracked Fingernails can already cause damage and therefore a straight in the area of budgetary resources lead to undesirable consumer frustration. Bags and pillows Films also have the disadvantage that these sealed seams or circumferential seams have that can leak. In addition, the for the production of Pouches and pillows can not be used or only very much convert it into other geometric shapes. This is how balls are released Do not manufacture film tubes in one work cycle. There are also foil bags and foil pillows are not dimensionally stable. If there is a deformation force, take bags and pillows made of deformable foils in the unfilled and filled state original form, d. H. before applying force, no longer independently.

The publication DE-A 20 65 153 describes several components comprising surfactant Shaped body consisting of an outer casing made of sodium silicate and enclosed therein Detergent components exist. The silicate shell is made by printing in two Hemispheres produced, which after filling the sufficient for a wash cycle Amount of detergent components assembled and to the shaped body get connected. The process is extremely impractical and leads to useless Laundry detergent portions.

The document DE-A 20 07 413 describes detergent moldings made from a core from one or more detergent component (s) and a shell made of molded, Shell material consisting predominantly of sodium metal silicate. The pressing of the Envelope material to half-shells and the filling and welding of the half-shells the finished molding requires complex technology, and many of the moldings break before they get into the washing process.

The publications DE-A 198 34 181, DE-A 198 34 180 and DE-A 198 34 172 describe detergents, dishes, care products or cleaning / decalcifying agents Preparations from one made by pressing, from two equal halves existing tablet from one or more detergents, care products or Detergent components and one with an additional if necessary Hollow body with and without compartments provided core from another Detergent, care and cleaning agent components. Apart from that The fact that, even in this case, the production only takes place in a complicated, multi-stage process can only be a solid core in the tablet Work in hollow bodies with and without compartments, if not premature dissolving the tablet is to be initiated from the inside.

The methods known in the prior art for producing hollow bodies, in particular hollow articles containing detergents, cleaning agents and / or care products, such as described for example in WO-A1 01/36290, on the one hand have the disadvantage that the hollow bodies produced are rigid, d. H. are not flexible and / or elastic, so that when used in the washing and / or cleaning liquor during the dissolving process, sharp-edged walls can arise that can damage textiles.

Second, a rigid, dimensionally stable body prevents the in Compartment containing agent, since this in contrast to a flexible body, not compressible or without great effort after opening is compressible.

Third, such hollow bodies are made using one or more compartments Injection molding process, this process is extremely expensive. Moreover can be practically only by means of injection molding without complex forced demolding Half body, d. H. do not produce essentially closed bodies. At least two half-bodies must then be connected in a further step or by means of a film are closed to form a closed body. A simple mass production of spherical bodies in an injection molding tool, d. H. in one cycle, is practically impossible.

Injection molding process as described in WO-A1 01/36290, thermoforming process as described in WO-A1 00/55068 or the use of films, have further the disadvantage that one cannot use these processes in a single work cycle can produce closed hollow bodies with one or more compartments that have flexible, preferably elastic, walls. You can also go to Using the same preform does not have almost any geometric shapes Form hollow bodies in a cycle, such as a spherical shape, bottle shape, animal figure, Santa Claus or the like, without having to be forced to demold or the resulting half-body must connect to form a hollow body.

The object of the invention was therefore a technically simple and fast method for Production of a water-soluble hollow body, in one cycle if possible, containing one Agents, in particular a detergent, cleaning agent or care agent, are available to provide, which overcomes the aforementioned disadvantages in the prior art. The The invention was further based on the task of detergents, cleaning agents or Separate care product components from each other and still in the same portion of detergent, cleaning agent or care agent, with the aim of a mass exchange or a mutual impairment, which under Circumstances associated with loss of activity can be as low as possible hold. This would also have the advantage that the storage stability of detergent, Detergent or care product preparations could be increased significantly and the content of active substance could also be reduced in individual cases because in the prior art when calculating them due to an expected Loss of activity of individual components is always an overdose had to become.

Surprisingly, it has now been found that water-soluble, can produce flexible, preferably elastic hollow bodies, the means, in particular Detergent, detergent and / or maintenance portions. It was also found the water-soluble, flexible, preferably elastic, hollow body in practically any shape, the separate Compartment (s) can have, manufactured using the blow molding process compared to injection molding, thermoforming, deep drawing or the same, has significant procedural advantages. Besides, that is Blow molding process saves material because there are no crushed edges or other protruding parts or excess parts must be removed from the blow-molded hollow body.

• a) Urformen eines Vorformlings aus einer Blasformmasse basierend auf einem wasserlöslichen polymeren Thermoplast;
• b) Blasformen des Vorformlings zu einem Hohlkörper;
• c) Füllen des Hohlkörpers mit mindestens einem Mittel, bevorzugt Wasch-, Pflege- und/oder Reinigungsmittel; und
• d) flüssigkeitsdichtes Verschließen des blasgeformten Hohlkörpers;
• e) wobei der mit mindestens einem Mittel oder Glycerin als Prüfmittel gefüllte und/oder unbefüllte blasgeformte Hohlkörper
  • a) bei einer Dehnung entlang seiner längsten Achse eine Streckspannung von zwischen ≥ 3 N/mm² und ≤ 15 N/mm² aufweist, und/oder
  • b) bei einem Stauchweg von 22 mm senkrecht, mittig, in Richtung seiner kürzesten Achse eine Verformungsarbeit von zwischen ≥ 0,05 Nm und ≤ 5 Nm auftritt, und/oder
  • c) bei einer Kraft F₁ > 0,1 N und ≤ 500 N längs eines Weges s₁ verformbar ist und nach Wegfall der Krafteinwirkung in Richtung der ursprünglichen Form zurückkehrt, und/oder
  • d) nach Wegfall einer Verformungskrafteinwirkung eine Rückstellgeschwindigkeit v von zwischen > 0,01 mm/min und ≤ 650 mm/min aufweist, und/oder
  • e) das Elastizitätsmodul der Hohlkörperwand des mittels Blasformung hergestellten flexiblen ungefüllten oder mit Mittel, vorzugsweise Glycerin, zu ≥ 80 Vol.-% gefüllten Hohlkörpers ≤ 1 GNm², vorzugsweise ≤ 0,1 GNm², bevorzugt ≤ 0,01 GNm² beträgt, und/oder
  • f) bei einem mit Mittel zu ≥ 80 Vol.% gefüllten blasgeformten Hohlkörper ein Stauchwiderstand F_max von zwischen ≥ 20 N und ≤ 2000 N, auftritt.

The invention relates to a method for producing a flexible, preferably elastic, water-soluble hollow body, comprising an agent, in particular a washing, care and / or cleaning agent, comprising the steps:

• a) preforming a preform from a blow molding compound based on a water-soluble polymeric thermoplastic;
• b) blow molding the preform into a hollow body;
• c) filling the hollow body with at least one agent, preferably washing, care and / or cleaning agent; and
• d) liquid-tight sealing of the blow-molded hollow body;
• e) the blow-molded hollow body filled and / or unfilled with at least one agent or glycerol as the test agent
  • a) has a yield stress of between ≥ 3 N / mm ² and ≤ 15 N / mm ² when stretching along its longest axis, and / or
  • b) with a compression path of 22 mm vertically, centrally, in the direction of its shortest axis, a deformation work of between ≥ 0.05 Nm and ≤ 5 Nm occurs, and / or
  • c) at a force F ₁ > 0.1 N and ≤ 500 N is deformable along a path s ₁ and returns in the direction of the original shape after the loss of force, and / or
  • d) after the loss of a deformation force, a return speed v of between> 0.01 mm / min and ≤ 650 mm / min, and / or
  • e) the modulus of elasticity of the hollow body wall of the flexible unfilled hollow body or filled with agents, preferably glycerol, to ≥ 80% by volume is ≤ 1 GNm ² , preferably ≤ 0.1 GNm ² , preferably ≤ 0.01 GNm ² , and or
  • f) a compression resistance F _max of between ≥ 20 N and ≤ 2000 N occurs in a blow-molded hollow body filled with an agent of ≥ 80 vol.%.

• a) in einem ersten Schritt mittels Extrudieren ein Vorformling herstellt, und
• b) in einem zweiten Schritt in einem Arbeitszyklus der Hohlkörper, vorzugsweise mittels eines unter Druck stehenden Gases, vorzugsweise Pressluft, geblasen, vorzugsweise zur endgültigen Hohlkörpergeometrie und mit dem Mittel, insbesondere einem Wasch-, Pflege- und/oder Reinigungsmittel gefüllt, flüssigkeitsdicht verschlossen, sowie anschließend entformt wird.

The invention further relates to a method for producing according to one of the preceding claims, wherein

• a) producing a preform in a first step by means of extrusion, and
• b) in a second step in a working cycle, the hollow bodies are blown, preferably by means of a pressurized gas, preferably compressed air, preferably to the final hollow body geometry and filled with the agent, in particular a detergent, care and / or cleaning agent, sealed liquid-tight, and is then demolded.

• - man wenigstens eine Waschmittel-Portion des Wasch- und/oder Reinigungsmittel enthaltenden Hohlkörpers nach einem der vorherigen Ansprüche in die Waschmaschine, insbesondere in die Einspülkammer und/oder Waschtrommel, eingibt;
• - man die gewünschten Waschbedingungen einstellt; und
• - bei Eintreten dieser Bedingungen sich der Hohlkörper und/oder die Kompartimente in der wässrigen Umgebung öffnet und die waschaktive(n) Zubereitung(en) der Waschmittel-Portion in die Waschflotte abgibt, so dass diese mit dem zu waschenden Gut in Kontakt kommt.

The invention also relates to a washing method, in particular a method for machine washing in a commercially available washing machine, which comprises the steps that

• - at least one detergent portion of the detergent and / or cleaning agent-containing hollow body according to any one of the preceding claims in the washing machine, in particular in the dispenser and / or washing drum;
• - the desired washing conditions are set; and
• - When these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the wash-active preparation (s) of the detergent portion into the wash liquor so that it comes into contact with the items to be washed.

• - man wenigstens eine Reinigungsmittel-Portion des Wasch- und/oder Reinigungsmittel enthaltenden Hohlkörpers nach einem der vorherigen Ansprüche in die Reinigungsflotte eingibt;
• - man die gewünschten Reinigungsbedingungen einstellt; und
• - bei Eintreten dieser Bedingungen sich der Hohlkörper und/oder die Kompartimente in der wässrigen Umgebung öffnet und die reinigungsaktive(n) Zubereitung(en) der Reinigungsmittel-Portion in die Reinigungsflotte abgibt, so dass diese mit dem zu reinigenden Gut in Kontakt kommt.

The invention also relates to a cleaning process comprising the steps of

• - At least one detergent portion of the detergent and / or cleaning agent-containing hollow body according to one of the preceding claims is added to the cleaning liquor;
• - you set the desired cleaning conditions; and
• - When these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the cleaning-active preparation (s) of the detergent portion into the cleaning liquor so that it comes into contact with the items to be cleaned.

• - man wenigstens eine in dem Hohlkörper und/oder Kompartimenten enthaltende Spülmittel-Portion nach einem der vorherigen Ansprüche in die Geschirrspülmaschine, insbesondere in deren Einspülkammer und/oder in deren Spülraum eingibt;
• - man die gewünschten Spülbedingungen einstellt; und
• - bei Eintreten dieser Bedingungen sich der Hohlkörper und/oder die Kompartimente in der wässrigen Umgebung öffnet und die spülaktive(n) Zubereitung(en) der Spülmittel- Portion in die Spülflotte abgibt, so dass diese mit dem zu reinigenden Gut in Kontakt kommt.

The invention also relates to a washing method, in particular a method for machine washing in a commercially available dishwasher, which comprises the steps of

• - at least one detergent portion contained in the hollow body and / or compartments according to one of the preceding claims is introduced into the dishwasher, in particular into its washing-up chamber and / or into its washing compartment;
• - the desired rinsing conditions are set; and
• - When these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the active wash (s) of the detergent portion into the wash liquor so that it comes into contact with the items to be cleaned.

Cleaning agents in the sense of this invention also include detergents.

Blow molding methods suitable according to the invention include extrusion blow molding, Coextrusion blow molding, injection stretch blow molding and immersion blowing.

The hollow body according to the invention with and without compartments can preferably be "turn inside out", d. H. it can be pushed through in such a way that the original inside to the outside and vice versa. This flexibility leads to that compared to rigid Shaped bodies particularly increased resistance to leakage under pressure, to avoid stress cracks or breakage.

The hollow bodies according to the invention dissolve completely in water or in essentially on, in this way the in the closed hollow body and / or agents contained in the compartments are released to the environment. For example, the agents containing the process according to the invention Hollow bodies in an aqueous machine washing, cleaning or care process be used. Preference is given to using those produced according to the invention Hollow bodies in standard washing machines or dishwashers. On Use of the hollow body according to the invention in hand basins or in a bowl is also possible. Important for the release of the in the hollow body / compartments contained agent is an aqueous environment surrounding them from the outside.

According to the invention, the hollow body and / or the compartments contain measured ones Quantities, d. H. Servings, at least one washing-active, cleaning-active or active care preparation, usually measured amounts of several wash-active, cleaning-active or nourishing preparations. It is possible that the Servings of only active washing, cleaning or caring preparations certain composition included. According to the invention, however, it is preferred that several, usually at least two, washing-active, cleaning-active or active care preparations of different compositions in the detergent, Detergent and / or maintenance portions are included. The composition With regard to the concentration of the individual components of the washing-active, cleaning-active or maintenance-active preparation (quantitative) and / or with regard to the Type of the individual components of the wash-active, cleaning-active or care-active Preparation (qualitatively) be different. It is particularly preferred that the Components are adapted in terms of type and concentration to the tasks that the Detergents, cleaning agents and / or care agent portions in the washing, Cleaning and / or maintenance process must be carried out.

Under the term "wash-active or cleaning-active or care-active preparation" Preparations of all conceivable, in the context of the present invention Related to a washing, cleaning and / or care process relevant Understood substances. In the case of detergents and cleaning agents, these are primarily those actual washing and / or cleaning agents with their in the further course of Description of individual components explained in more detail. This includes active substances such as Surfactants (anionic, nonionic, cationic and amphoteric surfactants), Builders (inorganic and organic builders), bleaches (such as for example peroxo bleach and chlorine bleach), bleach activators, Bleach stabilizers, bleach catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and fragrances (Perfumes) without the term being restricted to these substance groups.

However, under the term "active washing or cleaning preparations" washing aids and cleaning aids including rinsing aids are also understood. Examples of these are optical brighteners, UV protection substances, so-called soil repellents, that is polymers that re-contaminate fibers or hard surfaces counteract (including dishes), as well as silver preservatives, colorants and Dye removers. Also care products, such as laundry treatment products, in particular Fabric softener or dish care additive additives such as rinse aid are used according to the invention as wash-active or as cleaning-active or as care-active preparations.

According to the detergent, cleaning agent or care agent portions in one or more flexible, preferably elastic, hollow body (s) and / or one or contain more compartments. The exact shape of the hollow body is in this Context just as critical as its size; only default is in this regard, that shape and size are in accordance with later use stand, i.e. use in a washing, cleaning and / or care process, especially in conventional washing machines or dishwashers. Are conceivable Hollow bodies in spherical, ellipsoidal, cube, cuboid, trapezoidal, conical or pyramidal or trochoid form; cuboid or trochoidal hollow bodies have well proven according to the invention and can therefore be used with advantage. At the Most preferred are spherical hollow bodies, in particular spheres.

In preferred embodiments of the invention, the size of the hollow body is such that that the hollow body in the dispenser of a commercial washing machine or Dishwasher, in the laundry running nets or sacks or the like can be. Particularly preferred embodiments of the invention Detergent, detergent or care agent portions exceed a length (longest axis) of 10 cm not, while the sizes of the width and height clearly are lower, for example 1 to 5 cm.

Flexible hollow bodies in the sense of this invention also include elastic ones Hollow body.

The term "elastic hollow body" is understood in particular to mean that the shaped articles containing the detergents, in particular detergents, cleaning agents and / or care products, have an inherent dimensional stability which enables them under the usual conditions of manufacture, storage, transport and handling to have a structure which does not collapse and which is stable against breakage and / or pressure by the consumer, the unfilled and / or filled with at least one agent, preferably glycerol, blow-molded hollow body with an elongation along its longest axis a yield stress of between ≥ 3 N / mm ² and ≤ 15 N / mm ² , and / or with a compression path of 22 mm vertically, centrally, in the direction of its shortest axis, a deformation work of between ≥ 0.05 Nm and ≤ 5 Nm occurs, and / or with a force F ₁ > 0.1 and ≤ 500 N is deformable along a path s ₁ and after the loss of force in the direction of the original n shape returns, or assumes the original shape completely or almost completely after the loss of force, and / or has a return speed v of between> 0.01 mm / min and ≤ 650 mm / min after the loss of a deformation force, and / or the modulus of elasticity the hollow body wall of the flexible unfilled hollow body produced by means of blow molding or filled with agents, preferably glycerol, to 80 80% by volume ≤ 1 GNm ² , preferably 0,1 0.1 GNm ² , preferably 0,0 0.01 GNm ² , and / or at a compression molded F _max of between ≥ 20 N and ≤ 2000 N occurs in a blow-molded hollow body filled with agent, preferably glycerol, to 80% by volume.

According to the invention, it is of no influence whether this structural stability results from the due to various properties resulting from the following parameters of the flexible, preferably elastic, hollow body alone and / or from the Presence of compartmentalization devices and / or from the filling with wash-active, cleaning-active and / or care-active preparations results. In preferred embodiments of the invention already have the flexible, preferably elastic, hollow body itself has sufficient inherent dimensional stability as this advantageous on the mobility in machines in the manufacture of the hollow body and the Filling during the production of the detergent, Servings of detergent or care products.

The pressure resistance of the flexible, preferably elastic, blow-molded hollow body According to the invention, the measurement is carried out in the usual way such that unfilled and, if appropriate, closed compartments provided with compartments Hollow body at room temperature an internal, steadily increasing vacuum is applied until the hollow body begins to collapse. The inherent dimensional stability of the Hollow bodies should particularly preferably be such that in the case of such vacuum collapse Tests of unfilled and, if necessary, provided with compartmentalization devices Hollow bodies do not collapse before reaching a vacuum of 900 mbar, preferably starts from 750 mbar and in particular from 500 mbar, insofar the hollow bodies used according to the invention differ fundamentally from films or so-called "pouches", such as those used to provide detergents, Detergents or care products can also be used. These collapsing even at a pressure that is only slightly below atmospheric pressure. In Similarly, the flexible, preferably differ according to the invention elastic, but also hollow body (subsequently applied to molded body) Coatings. The hollow bodies according to the invention are independent, self-supporting Hollow bodies with and without compartments, which are usually already before filling with one or more wash-active, care-active or cleaning-active Component (s) exist and is then filled. In contrast to that Coatings on existing moldings (e.g. compacts, granules, extrudates etc.) applied and then dried or cured; only then do they form one Hollow bodies surrounding molded bodies with and without compartments.

It is particularly preferred according to the invention if the walls of the hollow bodies used according to the invention continue to form a good diffusion barrier, in the same way as the compartments to be explained in detail later, in particular for the detergent-active, detergent-active or care-active preparations, in particular gaseous substances and especially water vapor. Diffusion of water vapor should preferably be possible in a maximum amount of 350 g / (m ² .24 h), more preferably only in an amount in the range of a maximum of 100 g / (m ² .24 h), even more preferably in one Quantity of maximum 50 g / (m ² .24 h).

The empty hollow body with and without compartments of the invention portioned agents can be at least partially reversible by applying force deform and shows a certain after the loss of force Reset speed. High reset speeds (e.g.> 2000 mm / min) are achieved by rigid bodies that are in the initial shape "spring back", provided they do not remain in the pressed state. This behavior of "jumping back" is undesirable, since in this way stress cracks in the Hollow bodies with and without compartments can arise, the product leakage enable. On the one hand, it is therefore necessary to have a low reset speed Ensure hollow bodies with and without compartments, on the other hand, the hollow body deform with and without compartments without breaking or cracks to get.

As mentioned above, the envelopes according to the invention should at least partially reversibly deformed (there would be no irreversible deformation Return speed measurable). In preferred embodiments of the present Invention, the deformation is completely reversible, i. H. they are according to the invention portioned detergents, dishwashing detergents or cleaning agents preferred, in which the unfilled Wrapping returns to its original shape after the force is removed.

The force F ₁ depends on the indentation depth, since the hollow body, with and without compartments, opposes increasing resistance to the penetrating body. First of all, it is important for the present invention that the hollow body with and without compartments can be deformed at all with a force of 500 N or less. In preferred embodiments of the present invention, the details relate to forces of the penetration depths of a round rod with a diameter of 8 mm, in particular of 10 mm in diameter, preferably of 15 mm in diameter, preferably of 20 mm in diameter and more preferably of 22 mm.

If the distance s _{1 is} defined, not only the force but also the deformation work can be exactly determined. When force is exerted by a round rod with a diameter of 8 mm and a penetration depth of S ₁ = 22 mm, the deformation work in the case of flexible, unfilled hollow bodies produced by means of blow molding is well below the values of comparable rigid unfilled bodies, in which deformation work of at least> 5 Nm must be done.

As mentioned above, the hollow bodies according to the invention should be with and without Allow compartments to be at least partially reversibly deformed (if irreversible Deformation would not be able to measure a return speed). In preferred Embodiments of the present invention, the deformation is completely reversible, d. H. portioned compositions according to the invention are preferred in which the unfilled Hollow bodies with and without compartments after the loss of force in their original form returns.

In an embodiment which is suitable according to the invention, the flexible, unfilled or Vol 80% by volume hollow body produced by blow molding is by a force F ₁ 500 500 N along a path s ₁ = 22 mm, in particular by a force F ₁ 100 100 N along a path s ₁ = 22 mm, preferably by a force F ₁ 60 60 N along a path s ₁ = 22 mm, preferably by a force F ₁ 40 40 N along a path s ₁ = 22 mm and more preferably by a force F ₁ ≤ 20 N along a path s ₁ = 22 mm, vertically, centrally, in the direction of the shortest axis of the hollow body, deformable.

Examination of the hollow bodies filled with medium with and without compartments, if not otherwise stated was carried out at temperatures of 20 ° C, the Hollow bodies with and without compartments, for example at ≥ 80% by volume, preferably with Glycerin was filled as the test medium.

It is advantageous if the flexible, unfilled or to ≥ 80 produced by blow molding Vol .-% filled with glycerol hollow bodies after the loss of force Reset speed v ≤ 650 mm / min. in particular v ≤ 500 mm / min. preferably v ≤ 100 mm / min. preferably v ≤ 50 mm / min. more preferably v ≤ 10 mm / min and particularly preferably v ≤ 1 mm / min. having.

The deformation work required to deform the flexible, unfilled hollow body produced by blow molding should be w ≤ 1.0 Nm along a path s ₁ = 22 mm, preferably w ≤ 0.75 Nm along a path s ₁ = 22 mm and preferably w ≤ 0, 50 Nm along a path s ₁ = 22 mm. To determine the deformation work, the deformation force w acts vertically, centrally, in the direction of the shortest axis of the hollow body.

The deformation work required to deform the flexible hollow body produced by blow molding, which is ≥ 80% by volume filled with glycerol, should be w ≤ 5.0 Nm along a path s ₁ = 22 mm, preferably w ≤ 2.5 Nm along a path s ₁ = 22 mm, preferably w ≤ 1 Nm along a path s ₁ = 22 mm, further preferably w ≤ 0.75 Nm along a path s ₁ = 22 mm and in particular w ≤ 0.5 Nm along a path s ₁ = 22 mm, be. To determine the deformation work, the deformation force w acts vertically, centrally, in the direction of the shortest axis of the hollow body.

Another variable for characterizing particularly preferred according to the invention portioned agent is the crush resistance. This can be in the form of a force-displacement Determine the diagram with commercially available tablet testing devices. For the interests of The present invention was a universal testing machine from Zwick type 1425 used.

The compression resistance is determined in accordance with DIN 55526 Part 1 in that Hollow body with and without compartments (= container) standing upright between the Plates of a pressure testing device is placed and compressed, the pressure force and the disk path is recorded until the required compression resistance and Disk path can be reached or by critical deformation or leakage of the A failure occurs.

The printing press was set to an upsetting speed of 10 mm / min. The test process was then started. The force [N] exerted on the portion at a penetration depth of 22 mm was printed out on the connected printer. The crush resistance is given in N. Here, hollow bodies containing portioned agent according to the invention with and without compartments are preferred, which are characterized in that the crushing resistance F _{max of} the hollow body containing portioned agent (= the filled hollow body with and without compartments) 20 to 2000 N, preferably 50 to 1000 N, particularly is preferably 75 to 600 N, more preferably 100 to 500 N and in particular 150 to 400 N. For test purposes, the hollow body produced by blow molding is filled with agents, preferably glycerol, with and without a compartment to ≥ 80% by volume.

The crushing resistance of the flexible, unfilled or made by blow molding ≥ 80 vol.% Hollow bodies filled with glycerin should be between 75 and 400 N, preferably from between 100 to 300 N and in particular from between 150 to 250 N be.

The modulus of elasticity of the hollow body wall of the flexible unfilled hollow body produced by blow molding or filled with glycerol to ≥80% by volume should be 1 1 GNm ² , preferably 0,1 0.1 GNm ² , preferably 0,0 0.01 GNm ² .

It is preferred according to the invention if the flexible, water-soluble, blow-molded Hollow body is integrally formed.

The wall thicknesses of the hollow body can be blow molded in some areas produce differently by changing the wall thickness of the preform, preferably along its vertical axis, correspondingly of different thicknesses, preferably through Regulation of the amount of thermoplastic material, preferably by means of a Adjusting spindle forms when the preform is removed from the extruder nozzle.

The hollow body can be used with areas of different outer circumference and Blow molding the constant wall thickness by changing the wall thickness of the preform, preferably along its vertical axis, correspondingly of different thicknesses, preferably by regulating the amount of thermoplastic material using a Adjusting spindle forms when the preform is removed from the extruder nozzle.

In this way, different geometrical configurations of the Blow molding hollow bodies with and without compartments. In a single cycle bottles, balls, Santa Clauses, Easter bunnies or other figures Blow molds that can be filled with agents, then sealed and then be demolded.

It is particularly advantageous that the hollow body is in the blow mold during blow molding emboss and / or decorate. By appropriately designing the blow mold, a motif can be mirrored onto the hollow body. That way shape the surface of the hollow body practically arbitrarily. For example, let Information such as calibration marks, application instructions, Apply danger symbols, brands, weight, filling quantity, expiry date, pictures etc.

The preform, the hollow body and / or the liquid-tightly closed hollow body one or more component (s), the component one or more Materials based on one or different water-soluble polymers Thermoplastics, comprises, exists.

The preform, the hollow body and / or the liquid-tightly closed hollow body can be tubular, spherical or bubble-shaped. Has a spherical hollow body preferably a shape factor of> 0.8, preferably of> 0.82, preferably> 0.85, more preferably> 0.9 and particularly preferably of> 0.95.

The shape factor in the sense of the present invention is modern Particle measurement techniques can be precisely determined with digital image processing. A common one The process is, for example, the Camsizer® system from Retsch Technology or that KeSizer® from Kemira. These methods are based on the fact that the hollow bodies or Bodies are irradiated with a light source and the hollow bodies as projection surfaces recorded, digitized and processed by computer technology. The determination of Surface curvature takes place by an optical measuring method, in which the "Shadow cast" of the hollow body to be examined is determined and in one corresponding form factor is converted. The underlying principle for Determination of the form factor was, for example, by Gordon Rittenhouse in "A visual method of estimating two-dimensional sphericity "in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pages 79-81. The measuring limits of this optical Analysis methods are 15 µm to 90 mm. Procedure for determining the Shape factors for larger particles are known to the person skilled in the art. These are based on the Rule on the principles of the above procedures.

The release from the hollow body with and without compartments can either be due to this can be achieved at different times that the blow molded walls have different dissolution or disintegration speeds. This is possible, for example, by choosing the material thickness.

The walls of the hollow body produced by blow molding and / or the Compartments way a wall thickness of between 0.05-5 mm, preferably of between 0.06-2 mm, preferably between 0.07-1.5 mm, more preferably from between 0.08-1.2 mm, more preferably between 0.09-1 mm and most preferred, from between 0.1-0.6 mm.

The filling opening of the hollow body after filling can be liquid-tight, preferably by material closure, preferably by means of thermal treatment, particularly preferably by sealing a hot spot.

The filling opening or openings of the hollow body can be advantageously through thermal treatment, preferably by fusing the walls to the Close the opening, especially with a jaw, to seal it liquid-tight.

It is particularly preferred if this is in the hollow body and / or the compartments containing detergents and / or cleaning agents as wash-active substances anionic surfactants and / or nonionic surfactants. It is even more preferred if this is in the hollow body and / or detergents and / or cleaning agents containing the compartments free of Is cationic surfactant and / or amphoteric surfactants.

The hollow body and / or compartments of the hollow body, which wash, cleaning and / or active care preparation can be used together to form the invention Detergent, cleaning agent and / or care agent portion can be connected. in this connection According to the invention, one is not bound to only two compartments connect. Rather, it is also possible to add further compartments and / or hollow bodies, which washing, cleaning and / or maintenance-active preparation in further Contain compartments to add. For reasons of process economy here, compartments and / or hollow bodies are preferred which are flat Have connecting surfaces. Of course you are not bound to it, just filled hollow bodies with and / without compartments with each other to the invention To combine detergent, cleaning agent or care agent portion. It is much more also possible and preferred, hollow bodies which are active in washing, cleaning or care Preparation contained in compartments (A) or (B), with further washing, Blow-molded containing cleaning and / or maintenance-active preparations To connect compartments and / or hollow bodies. Here in particular has that Connecting blow-molded hollow bodies with tablets is particularly advantageous proved.

The respective compartments of the water-soluble hollow body can with a different content and / or a different composition of washing, cleaning and / or maintenance-active substances can be filled.

The means produced by blow molding, in particular washing, care and / or Detergents containing water-soluble hollow bodies have 2 to 40 Compartments, preferably 2 to 4, more preferably 2 to 3 compartments.

It is preferred if the anionic surfactant content is between 3% by weight - 40% by weight, and the nonionic surfactant content of between 15% by weight - 65% by weight, based on the total proportion by weight of the washing contained in the hollow body and / or detergent, the content of anionic surfactant and nonionic surfactant is ≤ 100% by weight in total.

The in the blow molded hollow body and / or the respective compartments, as washing-active, cleaning-active, care-active substances can be cationic surfactants, amphoteric surfactants, builder substances, bleaching agents, bleach activators, Bleach stabilizers, bleach catalysts, enzymes, polymers, cobuilders, Alkalizing agents, acidifying agents, anti-redeposition agents, silver protection agents, Colorants, optical brighteners, UV protection substances, fabric softeners and / or rinse aids include.

However, it is also provided according to the invention that the blow-molded, water-soluble Contains hollow bodies and / or at least one compartment selected from the Group comprising pharmaceuticals, pesticides, food, detergents, Cleaning agents, care products, cosmetics, hair dyes, agrochemicals, fertilizers, Building materials and / or glue.

The hollow bodies according to the invention with and without compartments can in particular for agrochemicals such as fertilizers and crop protection agents, food and Food additives, animal feed, pharmaceuticals, colors and fragrances and / or the like are used.

The blow-molded, water-soluble hollow body and / or its compartments can contain practically every conceivable means. It is preferred that the water content of the agent ≤ 10 wt .-%, based on the total weight of the agent in the hollow body and / or Compartment.

Another requirement is, but need not, be that the hollow body is used for release in an aqueous environment. This can, but must not be restrictive for the selection of agents that can be used according to the invention are.

It is preferred if at least one compartment containing enzyme is free from bleach and / or at least one bleach-containing compartment is free of enzyme.

Blow molding can be used to produce at least one hollow body area and / or compartment area with at least one outer surface of between 0.01 mm ² and 10 cm ² , the wall thickness of this area being smaller than the wall thickness in order to ensure faster dissolution in an aqueous solution the adjacent area.

The wall thickness of the hollow body formed by means of blow molding and / or the Compartments should be designed so that that in the hollow body and / or in the Compartments containing agents, in particular washing and / or cleaning agents, in the aqueous application liquor within ≤ 5 min. preferably within ≤ 3 minute preferably within ≤ 1 min. is partially or fully released.

To determine the release time, the hollow bodies were used with and without a compartment in 10 liters of agitated water, stirrer speed ≥ 60 rpm. given, the water to 90 ° C, preferably to 60 ° C, more preferably to 40 ° C, still more preferably 30 ° C and particularly preferably at 20 ° C. The is further preferred Release time directly in the aqueous application liquor at least one standard washing machine and / or dishwasher determined.

It is advantageous if the wall thickness of the hollow body and / or the compartments by means of blow molding so that the in at least one hollow body and / or in enzymes containing at least one compartment at least partially in time or completely before that contained in the or at least one other compartment Bleach can be released into the aqueous application liquor.

The wall thickness of the hollow body and / or the compartments can be blow molded be formed so that in the hollow body and / or in at least one Enzymes containing the compartment at least partially or completely ≥ 60 s in time, preferably ≥ 120 s, more preferably ≥ 240 s and most preferably ≥ 360 s the bleaching agent contained in the or at least one other compartment in the aqueous application liquor is released.

The internal volume of the hollow body produced by blow molding and / or the Compartments can, for example, be between 0.5 ml and 2000 ml, preferably between 2 ml and 500 ml, preferably between 5 and 250 ml, more preferably from between 10 and 100 ml, more preferably between 20 and 75 ml and am most preferred between 40 and 50 ml.

The blow molded hollow body with and without compartments can do that Detergents, in particular washing, care and / or cleaning agents, in solid form, more liquid Form and / or gel form, preferably in the form of particles, suspensions, Emulsions, a homogeneous solution, pastes and / or in the form of transparent, preferably clearer, solutions can be added.

The hollow body according to the invention produced by means of blow molding and / or the Compartment (s) can be a multi-phase agent, in particular washing and / or Contain detergents, preferably a temporary two or three phase mixture, which forms separate phases when left standing and shakes itself through temporary, reversible, in one phase, for example in an emulsion, suspension or Dispersion can be transferred.

The multi-phase agent can in particular be a washing, care and / or cleaning agent be, which preferably comprises at least one aqueous and / or non-aqueous phase, preferably at least one non-aqueous phase being liquid or solid and particularly preferably at least one aqueous phase is in gel form.

This during blow molding to form the hollow body and / or the compartments The water-soluble thermoplastic used is preferably selected from the group comprising polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, polyvinyl pyrrolidone, Polyethylene oxide, gelatin, cellulose, starch and derivatives of the aforementioned substances, Polyvinyl alcohol (PVA), acetalized polyvinyl alcohol and / or mixtures of the The aforementioned polymers, with polyvinyl alcohol being particularly preferred.

The polyvinyl alcohols described above are commercially available 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, Mowiol® 8-88 and Clariant L648.

Further polyvinyl alcohols which are particularly suitable as material for the hollow bodies can be found in the table below:

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

This during blow molding to form the hollow body and / or the compartments Water-soluble thermoplastic used can also be selected from the polymers Group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, Polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of above polymers.

It is preferred if that during blow molding to form the hollow body and / or Compartments used water-soluble thermoplastic comprising a polyvinyl alcohol, whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably constitutes 81 to 89 mol% and in particular 82 to 88 mol%.

It is further preferred that the water-soluble thermoplastic used in the blow molding to form the hollow body and / or the compartments comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 up to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

In a further embodiment, the blow molding composition comprises the aforementioned Thermoplastics in quantities of at least 50% by weight, preferably at least 70 % By weight, particularly preferably of at least 80% by weight and in particular of at least 90 wt .-%, each based on the weight of the blow molding compound.

It is advantageous if the melt flow index of the blow molding material during Extrusion, measured in the first step at 10 kg punch load, between 1 and 30, preferably between 5 and 15, particularly preferably between 8 and 12 and / or the Melt flow index (MFI) of the blow molding compound, measured at 2.16 kg ram load, between 4 and 40, preferably between 5 and 20, particularly preferably between 8 and Is 15. Particularly suitable for blow molding in the context of the present invention Polyvinyl alcohol types are medium to highly viscous and have, for example, MFI values from 6-8 (at 230 ° C, 2.16 kg load, PVA blend from manufacturer Texas Polymers "Vinex 2034" or "2144") or 9-11 (at 190 ° C; 10 kg load, PVA blend "TP Vinex 5030 ").

The hollow bodies can be used to facilitate blow molding (that is, their manufacture) Plasticizers, d. H. Plasticizers. This can be especially true of Be advantageous if the material for the hollow body is polyvinyl alcohol or partially hydrolyzed polyvinyl acetate were chosen. As plasticizers have especially glycerin, triethanolamine, ethylene glycol, propylene glycol, diethylene or Dipropylene glycol, diethanolamine and methyldiethylamine have been proven.

It is advantageous if the blow molding compound plasticizer in amounts of at least> 0 % By weight, preferably of ≥ 10% by weight, particularly preferably of ≥ 20% by weight and in particular of ≥ 30% by weight, in each case based on the weight of the blow molding composition, contains.

The flexible, preferably elastic, water-soluble hollow body can have flange parts have and optionally by positive locking and / or material locking, preferably connected by welding to at least one other hollow shape and / or be closed.

The hollow body produced according to the invention by means of blow molding and / or the Compartments can be 20 to 100%, preferably 30 to 99%, particularly preferably 40 to 98% and in particular 50 to 95% of their volume with agents, especially detergents, care products and / or cleaning agents.

The blow-molded hollow body and / or the respective compartments of the water-soluble Hollow bodies can from any direction, for example from above, from the side and / or be filled from below.

The hollow body produced according to the invention by means of blow molding and / or its Compartments can contain at least one, preferably several, wash-active cleaning-active (s), rinsing-active (n), care-active (s), pharmaceutically active Preparation (s), Food, Plant Protection Products, Fertilizers, Building Materials, Hair treatment agents, personal care products, cosmetics, wallpaper paste or adhesive, for example in the form of powder, granules, extrudates, pellets, beads, tablets, tabs, Rings, blocks, briquettes, solutions, melts, gels, suspensions, dispersions, Emulsions, foams and / or gases, partially or completely filled.

The hollow body produced according to the invention by means of blow molding and / or its Compartment (s) is particularly preferably transparent and / or translucent.

The hollow body produced according to the invention by means of blow molding and / or its Compartment (s) preferably has no seam, in particular no sigle seam, none Crimped seam and / or no groove, in particular flange groove.

It is preferred if at least one wall of the hollow body is used during blow molding and / or at least one wall of at least one compartment in multiple layers formed.

It is also preferred if at least two layers of the Wall of the hollow body and / or at least two layers of at least one Compartments designed so that there is a space between the layers is trained.

In one embodiment of the method according to the invention, one can also Multiple hollow bodies are formed by using a preform several layers blow molding, with a space during the blow molding is formed between the layers, so that these layers are each separate Form hollow bodies or compartments. These separate hollow bodies or Compartments can be interconnected.

In the method according to the invention, one can be coextruded Generate preform with several layers, preferably 2 to 5, which then becomes one Hollow body is blow molded, in which at least one wall of the hollow body and / or with the at least one wall of at least one compartment is multilayered.

The water-soluble, flexible, preferably elastic, closed hollow bodies can contain at least one means, in particular a detergent, care and / or cleaning agent.

The agent containing, in particular detergents, care and / or cleaning agents Blow molding, water-soluble, flexible, preferably produced according to the invention elastic, closed hollow body can be used for treatment, healing, washing, care, stick, fertilize, for vermin control, for the treatment of plants and / or for Cleaning, especially for washing, rinsing and / or cleaning soft and / or hard surfaces can be used.

Further preferred embodiments contain detergents, cleaning agents and / or care agent portions, being in the in the hollow bodies or compartments servings contained by a - preferably controllable - water solubility of the Hollow body material at a certain time of washing, cleaning or Maintenance process or when a certain pH value or a certain value is reached Ion strength of the wash liquor or also due to other controllable events or Conditions can be fed into the aqueous liquor. The quality of the Materials as well as their quantity / strength take on these solubility properties direct influence. Materials for the hollow bodies are particularly preferred which are - a certain wall thickness, which also determines stability - for certain Temperatures, pH values, ionic strengths, or after a certain dwell time in the dissolve aqueous liquor. Such a release process can affect the hollow body as a whole capture or only a part of it, so that parts of the hollow body when adjusting solve a certain combination of parameters while other parts are not yet (but only later) or not solve at all. The latter can be different Quality of the material as well as by different amounts of material (thickness of the Wall) or different geometries of the hollow body can be achieved. For example, it is possible to access water through the hollow body geometry complicate and thus delay the release process. In another preferred Embodiment, it is possible to have walls of the hollow body of different thickness (nevertheless from the same material) and thus an earlier one in the thinner places To allow loosening. In also preferred embodiments, the walls the hollow body is made from materials of different water solubility, for example from polyvinyl alcohols (PVAL) with different residual acetate content. This leads to the formation of perforated walls that prevent water from entering the wall Hollow body and / or leakage of the dissolved or undissolved ingredients allow out of the hollow body.

Furthermore, it is possible that the materials of the walls of the flexible, preferably elastic, hollow body from a wash-active, cleaning-active or care-active Active ingredient, of which PVAL is an example as a builder, or contain one. In the latter case, for example, washing-active, cleaning-active or active care ingredients that are only present in the preparations in small amounts and their uniform incorporation into the material is therefore not unproblematic the wall of the hollow body or in part of the material of the wall of the hollow body, for example, one that is in the washing, cleaning and / or Care course in which the active ingredient is needed, incorporated and when loosening the material of the wall can be released into the fleet at the right time. On Examples of this may be fragrances that are used in the final phase of washing, cleaning and / or care process are desired, but also optical brighteners, UV Protective substances, dyes and other washing-active, cleaning-active or active care preparations. The basic principle of incorporating such (usually incorporated in small quantities) components in the materials that the detergent, cleaning agent and / or care agent portions form, is co-pending patent application 199 29 098.9 with the applicant the title "active ingredient portion pack", the disclosure of which by Reference is fully incorporated in the disclosure of the present application becomes.

In a special embodiment of the invention it is also possible for the walls the flexible, preferably elastic, hollow body, which detergent, Serving of detergent or care products, made of different materials exist, i.e. have a heterogeneous structure. For example, in one Wall of the hollow body-forming polymer material is not made of islands in the polymer soluble foreign material, for example from another polymer (with different water solubility) or even from a completely different substance (for example an inorganic or organic substance). examples for this are water-soluble salts such as sodium sulfate, sodium chloride, sodium carbonate, Calcium carbonate, etc .; organic acids such as citric acid, tartaric acid, Adipic acid, phthalic acid, etc .; Sugars such as maltoses, dextrose, sorbitol, etc .; zeolites; silicates; crosslinked, for example weakly crosslinked polymers such as Polyacrylates, cellulose esters, cellulose ethers such as carboxymethyl cellulose. Such one In particularly preferred embodiments of the invention, construction can be advantageous connected that the other substance dissolves in water faster than the polymer, which allows water to penetrate into the hollow body and thereby to accelerated release of washing-active, care-active or cleaning-active Contributes components of the portion. Overall, the entire shape is stable Hollow bodies dissolve faster than a molded body in such a packaging made of a pure polymer material. Similarly, it is possible to cover the walls of the Form hollow bodies from layers of two or more polymers, which in particular preferred embodiments can be chosen so that they are in terms of their properties (stability, heat resistance, water solubility, Gas barrier properties, etc.) optimally supplement.

In a particularly preferred embodiment of the invention, a detergent, Detergent and / or care agent portion a flexible, preferably elastic, hollow body from at least one wash-active, cleaning-active or care-active preparation completely or partially surrounding from one under Washing, cleaning or care conditions of the integrable, blow-molded material with at least one compartment, the compartment (s) comprising one or more wash-active, cleaning-active or care-active preparation (s) contains.

In the embodiment mentioned, the one hollow body comprises at least one Compartment, i.e. a chamber, inside. Such a chamber or a such a compartment is usually through walls (with only one compartment these are the walls of the hollow body) limited space. Inside the walls of the Flexible, preferably elastic, hollow body according to the invention can however, there are also several rooms. These can either be formed by that individual rooms are separated from each other by walls that are part of the present invention are referred to as "compartmentalization devices" and the same or different washing-active, care-active and / or cleaning-active Separate components or preparations from each other, or that various washing-active, care-active or cleaning-active components or Border compositions directly but do not mix. In such a case, the interfaces (phase interfaces) are quasi contiguous components or compositions Kompartimentierungs facilities. The chamber or the compartment becomes whole or partially, advantageously entirely, surrounded by the enclosure of a washing, Cleaning and / or care conditions of the integrable, blow-molded material, the forms the wall of the flexible, preferably elastic, hollow body. By doing Compartment or in the chamber is / are one or more washing-active, contain cleaning-active or maintenance-active preparation (s). In most Embodiments of the invention advantageously contain a compartment several washing-active, cleaning-active or care-active preparations; is conceivable but also the case of the presence of only one such preparation in one Compartment or in a chamber.

In a particularly preferred embodiment of the invention, the contains Hollow body inside several compartments or chambers, each one or contain more washing-active, cleaning-active or care-active preparation (s). Examples of this are cuboid or trochoidal, in particular spherical flexible, preferably elastic, hollow body, the two, three or four or even more Compartments each have one or more washing-active, cleaning-active or active care preparation (s). A great advantage of this embodiment The invention is that the various washing-active, cleaning-active or active care preparations can be distributed to the compartments as it is best for the special requirements. So components that can adversely affect their effectiveness (e.g. enzymes, Alkali, bleach etc.) or otherwise - for example due to the physical state - would mix together, for example solid and liquid components, be spatially separated from each other. On the other hand, it is possible to use components that optimally at different times of washing, cleaning or Care process should be released into the respective fleet, spatially from each other separate and add to the fleet at the optimum time.

The size and shape of the individual compartments within a flexible, preferably elastic, hollow body is not critical and can largely depend on the Necessities of the individual case can be eliminated. So for certain washing-active, active cleaning or care active preparations or mixtures thereof, which in larger quantities are present, larger compartments are provided than for Preparations that are only present in small quantities. In others, with advantage Embodiments of the invention that can be used can be mixtures of certain Preparations provided at the start of the washing, cleaning or care cycle and are present in certain quantities, from others or in other quantities required components are spatially separated and in compartments of others Size.

In a particularly preferred embodiment of a flexible, preferably elastic, hollow body with at least one, preferably several Compartment (s), the detergent, cleaning agent or care agent portion contained, two or more, one or more washing-active, cleaning-active or compartments of the hollow body containing active care preparation (s) comprises, which are arranged enclosing each other. The compartments with the / the washing-active, cleaning-active and / or care-active preparation (s) are therefore in the Hollow bodies are not arranged next to one another or one above the other, but one above the other enclosing, for example more or less concentric ("onion model") or more or less coaxial ("multilayer rod model") or such that the innermost Compartment is completely surrounded by the next outer one, if necessary again completely from the following, etc. In such a case, the wash-active, cleaning-active or care-active substances on the compartments be distributed so that it is the first in the washing, cleaning or care process required components in the outermost compartment are the first to be exposed to the ingress of water or liquor while (a) Component (s) required later in an interior compartment (s) is / are arranged and before the entry of water through the more outside Compartments will be protected. In the context of this embodiment, it is not required that the inner compartments be completely separated from the outer are enclosed; a partial enclosure is also within the scope of the present one Invention.

According to a further preferred embodiment, the invention relates at least to a detergent, detergent and / or maintenance portion flexible, preferably elastic, hollow body, the wall of the hollow body and / or the compartments at least one washing-active, cleaning-active and / or Care-active preparation includes that under washing, cleaning or care conditions is disintegrable. It is preferred if the for the production of the hollow body and / or Compartments and / or the blow molding material already used for washing, includes cleaning-active and / or care-active preparation, which is under washing, Cleaning and / or maintenance conditions can be disintegrated.

The size, shape and arrangement of the compartment (s) and the at least one wash-active, cleaning-active or care-active preparation be designed the same as in the context of the embodiments described above, i. H. one or more can be in a flexible, preferably elastic, hollow body Compartments of any shape and size, each with one or more washing-active, cleaning-active or maintenance-active preparation (s) can be arranged. In the present However, there are several such flexible, preferably elastic, hollow bodies present together.

It corresponds to a preferred embodiment if the two or more flexible, preferably elastic, hollow body made of several different Materials or (possibly similar) materials with different Properties exist that - with particular advantage - under washing, cleaning or Care conditions are disintegrable. Such materials of the hollow body (s) include, but are not limited to, one or more water-soluble Polymer (s), preferably one or more materials from the group (if appropriate acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, Cellulose, and their derivatives and their mixtures, further preferred (if appropriate acetalized) polyvinyl alcohol (PVAL).

Serial, parallel and / or concentric arrangements of hollow bodies and / or Compartments, preferably with walls of the same or different Materials as described above can preferably be blow molded produce, preferably, but not exclusively, by at least one Double and / or multiple and / or coextrusion blow mandrel used. It is preferred if the preforms are made of the same or different thermoplastics based.

In a further, likewise preferred embodiment, it is according to the invention from Advantage if the flexible, preferably elastic, hollow body (s) has one or more Materials from the group of polymers containing acrylic acid, polyacrylamides, oxazoline Polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and their Mixtures include.

• - Mischungen aus 50 bis 100% Polyvinylalkohol oder Poly(vinylalkohol - co - vinylacetat) mit Molekulargewichten im Bereich von 10.000 bis 200.000 g/mol und Acetatgehalten von 0 bis 30 Mol-%; diese können Verarbeitungszusätze wie Weichmacher (Glycerin, Sorbit, Wasser, PEG usw.), Gleitmittel (Stearinsäure und andere Mono-, Di- und Tricarbonsäuren), sogenannte "Slipmittel" (z. B. "Aerosil"), organische und anorganische Pigmente, Salze, Blasformmittel (Citronensäure- Natriumbicarbonat-Mischungen) enthalten;
• - Acrylsäure-haltige Polymere, wie z. B. Copolymere, Terpolymere oder Tetrapolymere, die mindestens 20% Acrylsäure enthalten und ein Molekulargewicht von 5.000 bis 500.000 g/mol besitzen; als Comonomere sind besonders bevorzugt Acrylsäureester wie Ethylacrylat, Methylacrylat, Hydroxy-ethylacrylat, Ethylhexylacrylat, Butylacrylat, und Salze der Acrylsäure wie Natriumacrylat, Methacrylsäure und deren Salze und deren Ester wie Methylmethacrylat, Ethylmethacrylat, Trimethylammoniummethylmethacrylatchlorid (TMAEMC), Methacrylat-amidopropyltrimethylammoniumchlorid (MAPTAC). Weitere Monomere wie Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon sind ebenfalls mit Vorteil verwendbar;
• - Polyalkylenoxide, bevorzugt Polyethylenoxide mit Molekulargewichten von 600 bis 100.000 g/mol und deren durch Pfropfcopolymerisation mit Monomeren wie Vinylacetat, Acrylsäure und deren Salzen und deren Estern, Methacrylsäure und deren Salzen und deren Estern, Acrylamid, Styrol, Styrolsulfonat und Vinylpyrrolidon modifizierte Derivate (Beispiel: Poly-(ethylenglykol - graft - vinylacetat). Der Polyglykol-Anteil sollte 5 bis 100 Gew.-% betragen, der Pfropfanteil sollte 0 bis 95 Gew.-% betragen; letzterer kann aus einem oder aus mehreren Monomeren bestehen. Besonders bevorzugt ist ein Pfropfanteil von 5 bis 70 Gew.-%; dabei sinkt die Wasserlöslichkeit mit dem Pfropfanteil;
• - Polyvinylpyrrolidon (PVP) mit einem Molekulargewicht von 2.500 bis 750.000 g/mol;
• - Polyacrylamid mit einem Molekulargewicht von 5.000 bis 5.000.000 g/mol;
• - Polyethyloxazolin und Polymethyloxazolin mit einem Molekulargewicht von 5.000 bis 100.000 g/mol;
• - Polystyrolsulfonate und deren Copolymere mit Comonomeren wie Ethyl-(meth-) acrylat, Methyl(meth-)acrylat, Hydroxyethyl(meth-)acrylat, Ethylhexyl(meth-)acrylat, Butyl(meth-)acrylat und den Salzen der (Meth-) Acrylsäure wie Natrium-(meth-)acrylat, Acrylamid, Styrol, Vinylacetat, Maleinsäureanhydrid, Vinylpyrrolidon; der Comonomer- Gehalt sollte 0 bis 80 Mol-% betragen, und das Molekulargewicht sollte im Bereich von 5.000 bis 500.000 g/mol liegen;
• - Polyurethane, insbesondere die Umsetzungsprodukte von Diisocyanaten (z. B. TMXDI) mit Polyalkylenglykolen, insbesondere Polyethylenglykolen des Molekulargewichts 200 bis 35.000, oder mit anderen difunktionellen Alkoholen zu Produkten mit Molekulargewichten von 2.000 bis 100.000 g/mol;
• - Polyester mit Molekulargewichten von 4.000 bis 100.000 g/mol, basierend auf Dicarbonsäuren (z. B. Terephthalsäure, Isophthalsäure, Phthalsäure, Sulfoisophthalsäure, Oxalsäure, Bernsteinsäure, Sulfobernsteinsäure, Glutarsäure, Adipinsäure, Sebacinsäure usw.) und Diolen (z. B. Polyethylenglykole, beispielsweise mit Molekulargewichten von 200 bis 35.000 g/mol);
• - Celluloseether/ester, z. B. Celluloseacetate, Cellulosebutyrate, Methylcellulose, Hydroxypropylcellulose, Hydroxyethylcellulose, Methylhydroxypropylcellulose usw.;
• - Polyvinylmethylether mit Molekulargewichten von 5.000 bis 500.000 g/mol.

One or more materials can be mentioned with particular advantage from the following exemplary, but not restrictive list:

• - Mixtures of 50 to 100% polyvinyl alcohol or poly (vinyl alcohol - co - vinyl acetate) with molecular weights in the range from 10,000 to 200,000 g / mol and acetate contents from 0 to 30 mol%; these can include processing additives such as plasticizers (glycerin, sorbitol, water, PEG etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called "slip agents" (e.g. "Aerosil"), organic and inorganic pigments, Contain salts, blowing agents (citric acid-sodium bicarbonate mixtures);
• - Acrylic acid-containing polymers, such as. B. copolymers, terpolymers or tetrapolymers which contain at least 20% acrylic acid and have a molecular weight of 5,000 to 500,000 g / mol; as comonomers, particularly preferred are acrylate such as ethyl acrylate, methyl acrylate, hydroxy ethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and salts and esters thereof such as methyl methacrylate, ethyl methacrylate, Trimethylammoniummethylmethacrylatchlorid (TMAEMC), methacrylate-amidopropyltrimethylammoniumchlorid (MAPTAC). Other monomers such as acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone can also be used with advantage;
• - Polyalkylene oxides, preferably polyethylene oxides with molecular weights of 600 to 100,000 g / mol and their derivatives modified by graft copolymerization with monomers such as vinyl acetate, acrylic acid and their salts and their esters, methacrylic acid and their salts and their esters, acrylamide, styrene, styrene sulfonate and vinyl pyrrolidone (example : Poly (ethylene glycol - graft - vinyl acetate) The polyglycol content should be 5 to 100 wt .-%, the grafting content should be 0 to 95 wt .-%, the latter can consist of one or more monomers a graft fraction of 5 to 70% by weight; the water solubility decreases with the graft fraction;
• - Polyvinylpyrrolidone (PVP) with a molecular weight of 2,500 to 750,000 g / mol;
• Polyacrylamide with a molecular weight of 5,000 to 5,000,000 g / mol;
• - Polyethyloxazoline and polymethyloxazoline with a molecular weight of 5,000 to 100,000 g / mol;
• - Polystyrene sulfonates and their copolymers with comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and the salts of (meth) ) Acrylic acid such as sodium (meth) acrylate, acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone; the comonomer content should be 0 to 80 mol% and the molecular weight should be in the range of 5,000 to 500,000 g / mol;
• - Polyurethanes, in particular the reaction products of diisocyanates (e.g. TMXDI) with polyalkylene glycols, in particular polyethylene glycols with a molecular weight of 200 to 35,000, or with other difunctional alcohols to give products with molecular weights of 2,000 to 100,000 g / mol;
• - Polyesters with molecular weights of 4,000 to 100,000 g / mol, based on dicarboxylic acids (e.g. terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid, etc.) and diols (e.g. polyethylene glycols , for example with molecular weights of 200 to 35,000 g / mol);
• - Cellulose ether / ester, e.g. B. cellulose acetates, cellulose butyrates, methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, methyl hydroxypropyl cellulose, etc .;
• - Polyvinyl methyl ether with molecular weights of 5,000 to 500,000 g / mol.

In a further preferred embodiment of the invention, the two or several flexible, preferably elastic, hollow bodies made of two or more different materials consist, for example, of the above Materials can be selected, but can also include other materials. With In the case of the presence of several flexible, preferably, can be particularly advantageous elastic, hollow body the walls (= walls) of this hollow body from two or several similar materials, for example materials from the same Monomer building blocks, but materials with different properties, exist. Examples of this can be similar materials with different molecular weights (and therefore different solubility), PVAL materials with different Degree of acetalization (and thus different solubility or different Solution temperature in water), materials with different proportions grafted co-monomers or the like.

It corresponds to a further preferred embodiment that in the case in which several flexible, preferably elastic, hollow bodies are present, these flexible, preferably elastic, hollow body have different geometric shape. This can advantageously lead to different dissolving behavior or different kinetics of release of the in the compartment (s) of Contain the detergent, cleaning agent or care agent portion contained in the hollow body.

An embodiment of the detergent according to the invention is further preferred. Detergent or care agent portions in which the two or more flexible, preferably elastic, hollow body one - particularly preferred, but not mandatory detachable - form a bond. A composite of two or more flexible, preferably elastic, hollow bodies can be used with particular advantage if either detergent, detergent or care agent portions of different The composition should be dosed (e.g. heavy-duty detergent and colored detergent; in the latter, for example, are not bleaching components or are not in the same Concentration desired as in the former; the hollow body containing bleach could then be removed by the user if colorful laundry is to be washed) or if - For example, for small amounts of laundry or dishes - only a partial dose of in flexible, preferably elastic, hollow bodies containing detergent or Serving agent portion should be used. Such could be particularly preferred Bonding by gluing, fusing, welding or clamping the flexible, preferably elastic, hollow body can be produced; a mechanical Clamping also allows the bond to be loosened easily. In particularly preferred Embodiments of this type are composite hollow bodies again in an aqueous environment detachable from one another, for example by using a water-soluble adhesive; this could ensure that an automatic washing, cleaning or care process used composite completely dissolved and with the washing, Cleaning or rinsing liquor is withdrawn from the machine.

For the materials from which the compartments are made, the above information applies to the materials of the flexible, preferably elastic, Hollow body accordingly. In order to be reliable and simple In a preferred embodiment of the invention, the production method consists of Compartmentalization devices within the flexible, preferably elastic, Hollow bodies made of the same materials as the hollow bodies themselves. This allows the one-piece manufacture in one process step and makes the manufacturing process particularly economical.

In principle, however, it is also possible to use the materials of the facilities Compartment independent of the materials of the flexible, preferably elastic to select hollow body. This has the advantage of being special Requirements for the properties, for example water solubility, of Compartmentalization facilities can be taken into account.

In a preferred embodiment of the invention, the compartmentalization Facility (s) one (or more) reduced activity of at least one Component of a wash-active, cleaning-active or care-active preparation inhibiting device (s). Examples of this are all the cases where components washing-active, cleaning-active or care-active preparations under consideration a mutual impairment of their activity spatially separated from each other become. The compartmentalization facilities should then have properties that take these requirements into account, for example essentially impermeable for water vapor to keep bleach free of moisture, or should be acidic or be alkali-free to protect enzymes from premature breakdown. Such Inhibiting an activity reduction not only directly contributes to a better activity of the each protected component, but also allows the amounts of such Reduce components as an excess pending the usual Loss of activity is no longer required.

In other particularly preferred embodiments according to the invention, the is Compartmentierungseinrichtung (en) (a) the quality and / or quantity of Release of components of a washing-active, cleaning-active or maintenance-active Preparing institution (s). There may be cases where the Compartmentation devices have such a function, advantageously either components of the washing-active, cleaning-active or care-active Preparations at different times of washing, cleaning and / or Maintenance process can be handed over to the fleet (qualitative control), or it can different quantities of certain (qualitatively identical) preparations in the fleet are submitted (quantitative control).

In the former case, a flexible, preferably elastic, hollow body has For example, several compartments whose walls are different Have solubility (or temperature of dissolution) in water or in the liquor. The Compartments contain (washing, cleaning, care) active components for the first, second and possibly further (washing, cleaning, care) courses, the have different compositions and set them to different ones Times or at different temperatures of washing, cleaning or Care process free.

In the second exemplary case mentioned, the flexible, preferably elastic, Hollow bodies - just for example - walls and compartmentalization devices have, in which materials are incorporated that differ in different Solve temperatures or under different other boundary conditions. For example, small holes form in the compartment walls only weak mass exchange between individual compartments and the Allow outside environment and thus only small amounts of a washing-active, Add cleaning-active or maintenance-active preparation to the fleet; among other, later adjustable conditions, the holes or pores are enlarged because at solve soluble wall components in other conditions; through the larger holes can larger amounts of substance between the interior of the compartment (s) and the External environment (i.e. the fleet) and thus the desired ones higher concentrations of washing-active, cleaning-active or care-active Preparation can be discontinued in the fleet.

• - die Zeit, d. h. der Ablauf einer bestimmten Zeit, in der die Wände der flexiblen, vorzugsweise elastischen, Hohlkörper und/oder die Kompartimentierungs- Einrichtungen mit einem bestimmten Medium, beispielsweise mit einer wäßrigen Flotte, in Kontakt stehen, wobei eine zuverlässige Zeitsteuerung eine lineare Lösungskinetik voraussetzt;
• - die Temperatur, d. h. das Erreichen eines bestimmten Temperaturwertes im Verlauf des Temperaturprofils des Wasch-, Reinigungs- oder Pflegevorgangs; die Steuerung über die Temperatur stellt insbesondere bei Geschirrpflegemitteln wegen der mit jeder Stufe des Pflegevorgangs steigenden Temperatur eine zuverlässige und damit bevorzugte Ausführungsform dar;
• - der pH-Wert, d. h. die Einstellung eines bestimmten pH-Wertes im Verlauf eines Wasch-, Reinigungs- oder Pflegevorgangs durch Komponenten der waschaktiven, reinigungsaktiven oder pflegeaktiven Zubereitung oder das Verlassen eines bestimmten pH-Wertes nach Zerfall einer den pH-Wert beeinflussenden oder bestimmenden Komponente;
• - die Ionenstärke;
• - die mechanische Stabilität, welche - in Abhängigkeit von der Zeit, von der Temperatur oder von anderen Parametern - ein die Desintegration bestimmender Faktor sein kann;
• - die Permeabilität für eine bestimmte - vornehmlich gasförmige oder flüssige - Komponente; und dergleichen.

In particularly preferred embodiments, possible "switches" for the release of the components by the complementing devices are physicochemical parameters which bring about or control the disintegration of the compartmenting devices and / or the walls of the flexible, preferably elastic, hollow bodies. Examples include, but should not be construed as a limitation

• - The time, ie the expiry of a certain time in which the walls of the flexible, preferably elastic, hollow body and / or the compartmenting devices are in contact with a certain medium, for example with an aqueous liquor, with a reliable time control being a linear one Solution kinetics presupposes;
• - The temperature, ie the reaching of a certain temperature value in the course of the temperature profile of the washing, cleaning or care process; the control via the temperature represents a reliable and therefore preferred embodiment, in particular in the case of dish care products, because of the temperature rising with each stage of the care process;
• - the pH value, ie the setting of a certain pH value in the course of a washing, cleaning or care process by components of the washing-active, cleaning-active or care-active preparation or the leaving of a certain pH value after the disintegration of one which influences the pH value or determining component;
• - the ionic strength;
• - mechanical stability, which - depending on time, temperature or other parameters - can be a factor determining disintegration;
• - The permeability for a certain - primarily gaseous or liquid - component; and the same.

The aforementioned parameters are only examples that the invention does not should limit.

In a further preferred embodiment of the invention, the Compartmenting device (s) the activity of at least one component a washing-active, cleaning-active or maintenance-active preparation Device (s). This embodiment is particularly useful in such cases Wear in which it is required that the release of one or more active substances a washing-active, cleaning-active or maintenance-active preparation with one predetermined kinetics in the washing, cleaning or rinsing liquor. A special An example is a so-called "controlled release" release, which follows the above specified parameters on the properties of the wall of the flexible, preferably can control elastic, hollow body and / or the compartmentalization devices. In this way, a destructive influence of the fleet or the water alone can occur the active substance is reduced and the substance is actively added to the fleet over a longer period of time to be released.

It corresponds to a further preferred embodiment of the invention that one or several compartmentalization device (s) a part or the total amount at least one component of at least one active washing, cleaning active or active care preparation contains. This can be particularly advantageous achieved that one or more component (s) of at least one wash-active, cleaning-active or maintenance-active preparation in the material of the Compartmentation device is / are incorporated. Examples of such Substances have already been mentioned above in connection with the flexible preferably called elastic, hollow-forming material and include (are but not limited to) components in relatively small amounts in the Detergent, cleaning agent or care agent portions are included and therefore relatively poorly washable, cleaning active or in large batches Have active care preparations incorporated. A very simple familiarization succeeds in the materials of the compartmentalization facilities, and one can be made from them Reliable, controllable release in the course of washing, cleaning or Care process. With a suitable choice of materials, the release can also "controlled release" kinetics take place.

Another, also preferred embodiment of the invention is that one or more compartmentalization device (s) in part or in total at least one component of at least one active washing, cleaning active or care-active preparation. This is preferred because the Compartmentalization device not only the release kinetics influencing or even controlling components of detergents, cleaning agents or care agent portion according to the invention, but at the same time also as Component is involved in the success of the washing, cleaning or care process. Due to the large selection of materials available there are for them Embodiment numerous examples; Compartmentalization Facilities comprising (meth) acrylic acid and its derivatives (salts, esters) Polymers exist or include them.

According to a further preferred embodiment of the invention does the compartmentation device (s) consist of an interface between two adjoining components of a wash-active, cleaning-active or maintenance-active preparation or an interface between two adjoining wash-active, cleaning-active or care-active Preparations. This can be done in preferred embodiments of the invention For example, be the case if washing-active, cleaning-active or care-active Preparations by means of suitable measures, for example by coextruding in the Blow molding compound are processed, from which the preform then the hollow body is blow molded with and without compartments. In these cases you can activity-reducing or otherwise disadvantageous influences of the washing-active, cleaning-active or care-active preparations minimized one another or even be excluded. There is a possibility that either individual Components of a wash-active, cleaning-active or care-active preparation are combined to form adjacent interfaces or that wash-active, cleaning-active or care-active preparations, the mixtures of several Components are to be combined, forming interfaces. Both can be done in Frame of the flexible, preferably elastic, hollow body according to the invention Detergent, cleaning agent and / or care agent portions with special advantageous properties, for example with good release kinetics of the components in the aqueous fleets.

Another preferred embodiment of the invention consists in one or several flexible, preferably elastic, hollow body (s) with at least one Compartment containing detergent, cleaning agent and / or care agent portion, in which the flexible, preferably elastic, hollow body from an n delimiting There is surface, non-spherical hollow body, one of which is a surface assumes the function of a "lid" which is used to complete a process for Manufacture of the detergent, cleaning agent or care agent portions according to the Invention, d. H. after filling the compartment (s) inside the hollow body with one or more washing-active, cleaning-active or maintenance-active preparation (s), is applied while closing the hollow body. The "lid" is special preferably made of a material with controllable water solubility and can with the remaining hollow body with gluing, for example with a water-soluble adhesive, Fusion, welding or any other known method for Joining materials to be joined. This embodiment is for the Manufacture of detergents, cleaning agents or care agents according to the invention Portions particularly advantageous, since a gradual filling of the compartment (s) with one or more washing-active, cleaning-active or maintenance-active preparation is possible and the handling in later use for optimal results leads, in particular, to reliable control of the access of water or aqueous liquor for the interior of the flexible, preferably elastic, hollow body or Escaping washing-active, cleaning-active or maintenance-active preparation from the Inside of the blow molded hollow body.

The detergent, cleaning agent and / or care agent portions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, Builders, bleaches, bleach activators, enzymes, foam inhibitors, color and Fragrances as well - in the event that the detergent or cleaning agent portions at least in part as molded articles - binding and disintegration aids. These classes of substances are described below.

To develop the washing performance, the washing and Portion of detergent surfactants from the group of contain anionic, nonionic, zwitterionic or cationic surfactants, where anionic surfactants for economic reasons and because of their range of services are clearly preferred.

The portioned washing, care or cleaning agents according to the invention can be used as Detergents, as cleaning agents or as care products, each after what ingredients from the hollow body with and without compartments be enclosed. In addition to textile detergents, for example Detergent for machine or manual dishwashing, universal Manufacture household cleaners, toilet cleaners, glass cleaners, etc. Depending on the application can be the selection of ingredients in the washing, care or Detergent compositions within and with the hollow body Compartments exist to be different. Important ingredients of this Compositions are described below.

Contain the detergent, care and / or cleaning agent compositions preferably surfactant (s), anionic, nonionic, cationic and / or amphoteric surfactants are used. Are preferred from an application point of view in the case of textile detergents, mixtures of anionic and nonionic surfactants, where the proportion of anionic surfactants should be greater than the proportion of nonionic Surfactants. The total surfactant content of washing, care or Detergent composition is preferably below 30% by weight, based on the total mean.

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, 4 EO or 7 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 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks, but statistically. Such products can be obtained from the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which 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 formula I,


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 formula II


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

[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 portioned portions of the invention which are more suitable for textile washing Detergent, care or cleaning agent compositions on nonionic surfactants is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, each based on the total mean.

In machine dishwashing detergents, low-foaming agents are preferred non-ionic surfactants used. Particularly preferably contain inventive Dishwasher detergent is a nonionic surfactant that has a melting point above room temperature. Accordingly, preferred means are thereby characterized in that they have nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, included.

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 Pas, preferably above 35 Pas and in particular have above 40 Pas. 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. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, this is nonionic Surfactant with a melting point above room temperature 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 obtained 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 , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 moles, 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 up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene Have polyoxypropylene block copolymer units. The alcohol or alkylphenol part such nonionic surfactant molecules preferably make up more than 30% by weight, in particular preferably more than 50% by weight and in particular more than 70% by weight of the total Molecular weight of such nonionic surfactants. This makes them preferred rinse aids characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant make up, contain.

Other 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 of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per Moles of trimethylolpropane.

Nonionic surfactants that can be used with particular preference are for example under the name Poly Tergent® SLF-18 from Olin Chemicals available.

A further preferred portioned washing, care or cleaning agent according to the invention contains nonionic surfactants of 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 stands for a value of at least 15.

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

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

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

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

R ¹ 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.

If the last-mentioned statements are summarized, portioned washing, care or cleaning agents according to the invention are preferred, 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

contain, in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

In combination with the surfactants mentioned, anionic, cationic and / or amphoteric surfactants are used, these because of their Foaming behavior in machine dishwashing detergents is only of minor importance own and mostly only in amounts below 10 wt .-%, mostly even below from 5% by weight, for example from 0.01 to 2.5% by weight, in each case based on the agent, be used. The agents according to the invention can thus be used as a surfactant component also contain anionic, cationic and / or amphoteric surfactants.

The agents according to the invention can contain, for example, cationic compounds of the formulas III, IV or V 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 with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. 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 □ -sulfofatty acids (ester sulfonates), for. 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 Sulphonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 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.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol 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 in themselves 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 as well especially 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 surfactant content of preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20 % By weight, based in each case on the total composition.

In the context of the present invention, preferred agents additionally contain one or several substances from the group of builders, bleaches, bleach activators, enzymes, Electrolytes, non-aqueous solvents, pH adjusters, fragrances, perfume carriers, Fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, enema preventers, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, Fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and Impregnating agent, swelling and anti-slip agent as well as UV absorber.

As builders that can be contained in the agents 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.

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. Among the large number of commercially available phosphates have 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 gm. It has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water ,

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water (density 1 , 52 gcm ^-3 melting point 35 ° with loss of 5 H 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 gm. 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 dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ 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 terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the salt of water free of crystal water 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 + 2 KOH → 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 Are sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate usable 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 Na ₂ O: SiO ₂ modulus from 1: 2 to 1: 3, 3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide the sharp X-ray reflections that are typical of 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 through 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 aforementioned Substances, in the sense of this invention preferably the alkali carbonates, in particular Sodium carbonate, sodium bicarbonate or sodium sesquicarbonate used become.

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, washing, inventive Care or cleaning agents are preferred, which additionally contain one or more substances from the group of acidifying agents, chelating agents or coating 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 security are the fixed ones in particular Mono-, oligo- and polycarboxylic acids can be used. Again preferred from this group are 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 are closed to form rings by complex formation via an ion. The 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) are common complex-forming polymers Iminodiacetic 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 like Cellulose, starch or chitin are complex-forming polymers. In addition, you can this through polymer-analogous conversions with additional ligand functionalities be provided.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt,
• b) stickstoffhaltigen Mono- oder Polycarbonsäuren,
• c) geminalen Diphosphonsäuren,
• d) Aminophosphonsäuren,
• e) Phosphonopolycarbonsäuren,
• f) Cyclodextrine

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels, enthalten. In the context of the present invention, particular preference is given to washing, care or cleaning agents 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 Dishwashing detergent included.

• a) Polycarbonsäuren, bei denen die Summe der Carboxyl- und gegebenenfalls Hydroxylgruppen mindestens 5 beträgt wie Gluconsäure,
• b) stickstoffhaltige Mono- oder Polycarbonsäuren wie Ethylendiamintetraessigsäure (EDTA), N-Hydroxyethylethylendiamintriessigsäure, Diethylentriaminpentaessigsäure, Hydroxyethyliminodiessigsäure, Nitridodiessigsäure-3- propionsäure, Isoserindiessigsäure, N,N-Di-(β-hydroxyethyl)-glycin, N-(1,2- Dicarboxy-2-hydroxyethyi)-glycin, N-(1,2-Dicarboxy-2-hydroxyethyl)-asparaginsäure oder Nitrilotriessigsäure (NTA),
• c) geminale Diphosphonsäuren wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP), deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon und 1-Aminoethan-1,1-diphosphonsäure, deren höhere Homologe mit bis zu 8 Kohlenstoffatomen sowie Hydroxy- oder Aminogruppen-haltige Derivate hiervon,
• d) Aminophosphonsäuren wie Ethylendiamintetra(methylenphosphonsäure), Diethylentriaminpenta(methylenphosphonsäure) oder Nitrilotri(methylenphosphonsäure),
• e) Phosphonopolycarbonsäuren wie 2-Phosphonobutan-1,2,4-tricarbonsäure sowie
• f) Cyclodextrine.

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

• a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid,
• b) nitrogen-containing mono- or polycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic acid, N, N-di- (β-hydroxyethyl) 1,2-glycine Dicarboxy-2-hydroxyethyl) glycine, N- (1,2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA),
• c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), their higher homologues with up to 8 carbon atoms, and derivatives thereof containing hydroxyl or amino groups, and 1-aminoethane-1,1-diphosphonic acid, their higher homologues with up to 8 carbon atoms as well as derivatives thereof containing hydroxyl or amino groups,
• d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (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 - also monocarboxylic acids - understood in which the sum of carboxylic and in Molecule contained hydroxyl groups is at least 5. Complexing agent from the Group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. at the alkaline pH values of the treatment solutions required according to the invention these complex bilgeers are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of Use as salts are alkali, ammonium or alkylammonium salts, in particular Sodium salts, preferred.

Deposit-inhibiting polymers can also be used in the agents according to the invention be included. These substances, which can have different chemical structures, come from 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 be used in particular in the dishwasher detergents according to the invention Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, Dextrins, other organic cobuilders (see below) and phosphonates can be used. This Substance classes are described below.

Usable organic builders 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), provided that such use is not for ecological reasons objectionable, 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 , 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 have from 500 to 20,000 g / mol. Because of their superior solubility, can this 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 polyacrylates and also copolymers of unsaturated carboxylic acids containing sulfonic acid groups Monomers and optionally other ionic or nonionic monomers used. The copolymers containing sulfonic acid groups are discussed in detail below described.

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 contain. Further preferred copolymers are those which are preferred as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, 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 will be 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-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. there is a 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 used, the disodium salt neutral and the tetrasodium salt alkaline (pH 9) responding. Preferred aminoalkane phosphonates are Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) as well as their higher homologues in question. They are preferably in the form of neutral reacting 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 to use.

In addition to the substances from the substance classes mentioned, the Agents according to the invention further usual ingredients of washing, care or Contain cleaning agents, in particular bleach, bleach activators, enzymes, Silver preservatives, colors and fragrances are important. These substances will 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, phthaloiminoperic acid 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 of the number of carbon atoms mentioned and / or optionally 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 Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric 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 that 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 well suited 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. Enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from Cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic acting enzymes and cellulase, but especially protease and / or Mixtures containing lipase or mixtures with lipolytically active enzymes are particularly useful 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 the desired activities are set for the cellulases.

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

According to the state of the art, enzymes are primarily used Added preparation, in particular added to a tableware care product for the Main wash is determined. The disadvantage was that the optimum effect Enzymes used limited the choice of temperature and also problems with Stability of the enzymes occurred in a strongly alkaline environment. With the invention Detergent or detergent servings, it is possible to separate enzymes Introduce compartment and then use it in the pre-rinse cycle and thus the pre-rinse cycle in addition to the main rinse cycle for enzyme action To use soiling on the dishes.

It is therefore particularly preferred according to the invention that the one provided for the pre-rinse cycle active washing preparation or partial portion of a cleaning agent or care product Add portion of enzyme and then - more preferably - with such a preparation a water-soluble material of a flexible, preferably elastic, hollow body to include, for example, the enzyme-containing Protect preparation from loss of effectiveness due to environmental conditions. The Enzymes are further preferred for use under the conditions of Pre-care process, e.g. in cold water, optimized.

The detergent portions according to the invention can be advantageous if the enzyme preparations are in liquid form, as some of them are commercially available, because then a quick effect can be expected, which is already in the (relatively short and carried out in cold water). Even if - as usual - the Enzymes are used in solid form and these are encased in a hollow body are provided with a water-soluble material that is already soluble in cold water, can the enzymes their before the main wash or main cleaning Have an effect. Advantage of using a water soluble enclosure Material, especially cold water soluble material, is that the enzyme / Enzymes in cold water quickly take effect after dissolving the enclosure will come /. This means that their working time can be extended, which or washing result benefits.

The cleaning agents according to the invention for machine dishwashing can contain corrosion inhibitors to protect the dishes or the machine, whereby especially silver protection agents in the field of automatic dishwashing have special meaning. The known substances from the stand can be used of the technique. In general, silver protection agents can be selected from the group the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the Alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. you often finds active chlorine-containing agents in detergent formulations, which Can significantly reduce corroding of the silver surface. In chlorine-free cleaners organic and redox-active compounds containing oxygen and nitrogen, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these Classes of compounds. Also salt and complex inorganic compounds, such as Salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Are preferred here the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides cobalt or manganese and manganese sulfate. Zinc compounds can also be used can be used to prevent corrosion on the wash ware.

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

Non-aqueous solvents that are used in the agents according to the invention can come, for example, from the group of mono- or polyhydric alcohols, Alkanolamines or glycol ethers, provided they are in the specified concentration range Water are miscible. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerin, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, Ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, Dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl 3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Non-aqueous solvents can be used in the liquid detergents according to the invention Amounts between 0.5 and 10 wt .-%, but preferably less than 5 wt .-% and in particular below 3% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents may be indicated. All of them can be used here 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 means usually exceeds 5 % By weight of the total formulation is not.

In order to improve the aesthetic impression of the agents according to the invention, they can be dyed with suitable dyes. Preferred dyes, their selection the expert has no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agent and to light as well no pronounced substantivity towards textile fibers in order not to dye them.

As foam inhibitors that can be used in the agents according to the invention, For example, soaps, paraffins or silicone oils can be used, if appropriate can be applied to carrier materials. Suitable anti-redeposition agents that also referred to as soil repellents are, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of Methoxy groups from 15 to 30% by weight and hydroxypropyl groups from 1 to 15% by weight, each based on the nonionic cellulose ether and those from the prior art Technically known polymers of phthalic acid and / or terephthalic acid or 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 in the agents according to the invention can be added to cause graying and yellowing of the treated textiles remove. 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, whereby the ultraviolet absorbed from sunlight Light is emitted as a weak bluish fluorescence and with the yellow tone of the greyed or yellowed laundry produces pure white. Suitable connections originate, for example, from the substance classes of 4,4'-diamino-2,2'- stilbene disulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, 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, polyamides containing acidic groups are suitable for this purpose. Let continue soluble starch preparations and starch products other than those mentioned above use, e.g. B. degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose (Na- Salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as Methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and their mixtures in amounts of 0.1 to 5 wt .-%, based on the Means used.

The agents according to the invention are used as agents for automatic dishwashing assembled, so further ingredients can be used. On machine Dishwashed dishes are often subject to higher requirements than manually washed dishes. This is how dishes that are completely cleaned of leftovers become rated as not perfect if it is still after machine dishwashing whitish spots due to water hardness or other mineral salts which, due to the lack of wetting agents, comes from dried water drops. Around Maintaining crystal-clear and spotless crockery is therefore successfully used today Rinse aid. The addition of rinse aid at the end of the wash program ensures that the water runs as completely as possible from the wash ware, so that the different Surfaces at the end of the wash program are residue-free and spotlessly shiny. The mechanical cleaning of dishes in household dishwashers includes Usually a pre-wash, a main wash and a rinse cycle, by Intermediate rinse cycles are interrupted. For most machines that is Pre-wash for heavily soiled dishes can be activated, but is only possible in Exceptional cases chosen by the consumer, so that in most machines Main rinse, an intermediate rinse with pure water and a rinse be performed. The temperature of the main wash cycle varies depending on Machine type and program level selection between 40 and 65 ° C. Be in the rinse aid added rinse aid from a dosing tank in the machine, usually as Main ingredient contains non-ionic surfactants. Such rinse aids are more liquid Form before and are widely described in the prior art. Your job is there primarily in preventing limescale and deposits on the dishes.

The agents according to the invention can be formulated as "normal" cleaners, which together with commercially available supplements (rinse aid, regeneration salt) be used. With particular advantage, however, can with the invention Products without the additional dosage of rinse aid. This So-called "2in1" products lead to simplification of handling and relieve the consumer of the burden of adding two different doses Products (detergent and rinse aid).

Even when using "2in1" products, one is required to operate one Household dishwashers require two dosing processes at intervals, because after a certain number of rinsing the regeneration salt in Water softening system of the machine must be refilled. This Water softening systems consist of ion exchange polymers, the soft that of Soften the machine's incoming hard water and use it after the wash program a salt water rinse can be regenerated.

• a) ungesättigten Carbonsäuren
• b) Sulfonsäuregruppen-haltigen Monomeren
• c) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

enthalten. However, it is also possible to provide products according to the invention which, as so-called “3in1” products, combine the conventional cleaners, rinse aids and a salt replacement function. For this purpose, automatic dishwashing agents according to the invention are preferred which additionally comprise 0.1 to 70% by weight of copolymers

• a) unsaturated carboxylic acids
• b) monomers containing sulfonic acid groups
• c) optionally further ionic or nonionic monomers

contain.

These copolymers cause the dishes treated with such agents subsequent cleaning processes become significantly cleaner than dishes that are washed with conventional agents were rinsed.

As an additional positive effect, the drying time is reduced with that Detergent treated dishes on d. H. the consumer can after The cleaning program should take the dishes out of the machine earlier and use again.

The invention is characterized by an improved "cleanability" of the treated Substrates in later cleaning processes and by significantly shortening the Drying time compared to comparable agents without the use Polymers containing sulfonic acid groups.

The drying time in the context of the teaching according to the invention is generally the understood the meaning in the sense of the word, i.e. the time that passes until one in one Dishwasher-treated dish surface has dried, but in particular the time that elapses to 90% in with a detergent or rinse aid concentrated or diluted form treated surface is dried.

In the context of the present invention, unsaturated carboxylic acids of the formula VI are preferred as the monomer

R ¹ (R ² ) C = C (R ³ ) COOH (VI),

in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids that can be described by formula VI are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H; R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula VII

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VII),

in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH- C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas VIIa, VIIb and / or VIIc,

H ₂ C = CH-X-SO ₃ H (VIIa),
H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIb),
HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIIc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH- C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula VIIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula VIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIb), 3-methacrylamido-2-hydroxypropanesulfonic acid (X = -C (O) NH-CH ₂ OH (OH) CH ₂ - in formula VIIb), allylsulfonic acid (X = CH ₂ in formula VIIa), methallylsulfonic acid (X = CH ₂ in formula VIIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XVIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula VIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen-1-sulfonic acid (X = CH ₂ in formula VIIb), styrene sulfonic acid (X = C ₆ H ₄ in formula VIIa), vinyl sulfonic acid (X not present in formula VIIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - i n Formula VIIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula VIIb), sulfomethacrylamide (X = -C (O) NH- in formula VIIb), sulfomethyl methacrylamide (X = -C (O) NH-CH ₂ - in formula VIIb) and water-soluble salts of the acids mentioned.

Other ionic or nonionic monomers in particular are ethylenic unsaturated compounds. The content is preferably Polymers used according to the invention on monomers of group iii) less than 20 % By weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).

• a) ungesättigten Carbonsäuren der Formel VI.
  
  R¹(R²)C=C(R³)COOH (VI),
  
  in der R¹ bis R³ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• b) Sulfonsäuregruppen-haltigen Monomeren der Formel VII
  
  R⁵(R⁶)C=C(R⁷)-X-SO₃H (VII),
  
  in der R⁵ bis R⁷ unabhängig voneinander für -H -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH- C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• c) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt. In summary, copolymers are made of

• a) Unsaturated carboxylic acids of formula VI.
  
  R ¹ (R ² ) C = C (R ³ ) COOH (VI),
  
  in which R ¹ to R ³ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• b) Monomers of the formula VII containing sulfonic acid groups
  
  R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VII),
  
  in which R ⁵ to R ⁷ independently of one another are -H -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH- C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
• c) optionally further ionic or nonionic monomers

particularly preferred.

• a) einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• b) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln VIIa, VIIb und/oder VIIc:
  
  H₂C=CH-X-SO₃H (VIIa),
  H₂C=C(CH₃)-X-SO₃H (VIIb),
  HO₃S-X-(R⁶)C=C(R¹)-X-SO₃H (VIIc),
  
  in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH- C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• c) gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred copolymers consist of

• a) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid
• b) one or more monomers of the formulas VIIa, VIIb and / or VIIc containing sulfonic acid groups:
  
  H ₂ C = CH-X-SO ₃ H (VIIa),
  H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIb),
  HO ₃ SX- (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (VIIc),
  
  in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH- C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
• c) optionally further ionic or nonionic monomers.

The copolymers containing the agents according to the invention can comprise the monomers groups i) and ii) and optionally iii) in varying amounts, wherein all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined. Especially preferred polymers have certain structural units, the following to be discribed.

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula VIII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are produced by copolymerization of acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IX

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -CHC (O) -Y-SO ₃ H] _p - (IX),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Agents according to the invention which contain one or more copolymers are structural units of the formula X

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (X),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are also preferred, a preferred embodiment of the present invention, just like agents are preferred, which are characterized in that they contain one or more copolymers, the structural units of the formula XI

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XI),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XI

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XI),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XII

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas VII and / or VIII and / or IX and / or X and / or XI and / or XII

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VII),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (VIII),

- [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (IX),

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (X),

- [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -YSO ₃ H] _p - (XI),

- [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XII),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

In the polymers, the sulfonic acid groups can be neutralized in whole or in part Form, d. H. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and can be exchanged in particular for sodium ions. Appropriate means that are characterized in that the sulfonic acid groups in the copolymer partially or fully neutralized are preferred according to the invention.

The monomer distribution of those used in the agents according to the invention In the case of copolymers which contain only monomers from groups i) and ii), contain, preferably each 5 to 95 wt .-% i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight of monomer from the group ii), each based on the polymer.

In the case of terpolymers, those which contain 20 to 85% by weight of monomer are particularly preferred from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight Monomer from group iii) included.

The molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

The content of one or more copolymers in the agents according to the invention can vary depending on the application and the desired product performance, whereby preferred automatic dishwasher detergent according to the invention are that they contain the copolymer (s) in amounts of 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and contain in particular from 1 to 15% by weight.

As already mentioned above, the agents according to the invention are special preferably both polyacrylates and the copolymers described above unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers are used. The Polyacrylates have been described in detail above. Particularly preferred are combinations of the sulfonic acid groups described above Copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons. Such polyacrylates are commercially available under the trade name Sokalan® PA15 or Sokalan® PA25 (BASF) available.

The agents according to the invention can also be used as fabric softeners or washing additives be assembled. Depending on the intended use, others can Ingredients are used. Fabric softener compositions for rinse bath leveling are widely described in the prior art. Usually contain these Compositions as active substance a cationic quaternary ammonium compound, which is dispersed in water. Depending on the content of the finished Plasticizer composition of active substance is called diluted, ready-to-use products (active substance contents below 7% by weight) or so-called Concentrates (active substance content above 7% by weight). Because of the smaller volume and the associated reduced packaging and transport costs Textile incinerator concentrates have advantages from an ecological point of view and have become in the market enforced more and more. Due to the incorporation of cationic compounds, which are only slightly soluble in water are common Softener compositions in the form of dispersions have a milky cloudy appearance and are not translucent. For product aesthetics reasons it may also be desirable to provide the consumer with translucent, clear fabric softener To make available that stand out visually from the known products.

Contained portioned according to the invention as textile softening active substance Fabric softener preferably cationic surfactants, which are already detailed above have been described (formulas XII, XIII and XIV). Contain particularly preferably "Soft care portions" according to the invention, so-called esterquats. While there is one There are many possible compounds from this class of substances used according to the invention with particular preference esterquats, which are characterized by Implementation of trialkanolamines with a mixture of fatty acids and Dicarboxylic acids, optionally subsequent alkoxylation of the reaction product and Have quaternization produced in a manner known per se, as described in DE 195 39 846 is described.

The ester quats produced in this way are excellent for Production of portions according to the invention which are used as fabric softeners can. Depending on the choice of trialkanolamine, fatty acids and dicarboxylic acids as well as the quaternizing agent a variety of suitable products manufactured and in agents according to the invention can be used is a description of Esterquats preferably to be used according to the invention via their production route more precise than giving a general formula.

The components mentioned, the one to be used preferably Reacting esterquats can be used in varying proportions to each other become. In the context of the present invention, portioned fabric softeners are preferred in which a reaction product of trialkanolamines with a mixture of Fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which may be alkoxylated and then in a manner known per se was quaternized, in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-% is included. The use of is particularly preferred Triethanolamine, so that further preferred portioned fabric softener of the present Invention a reaction product of triethanolamine with a mixture of fatty acids and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, the optionally alkoxylated and then quaternized in a manner known per se in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight contain.

All fatty acids can be used in the reaction mixture to produce the esterquats Acids obtained from vegetable or animal oils and fats can be used.

The fatty acid in the reaction mixture can also be one at room temperature non-fixed, i.e. H. pasty to liquid, fatty acid can be used.

The fatty acids can be saturated or mono- or independently of their physical state be polyunsaturated. Of course, not only "pure" fatty acids are used, but also those obtained from fats and oils during the splitting technical fatty acid mixtures, these mixtures from an economic point of view are again clearly preferred.

So can in the reaction mixtures for the preparation of the ester quats for the clear aqueous fabric softener according to the invention, for example individual species or Use mixtures of the following acids: caprylic acid, pelargonic acid, capric acid, Lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol acid, Arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, 10- Undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, Linolaidic acid, α- and β-eläosterainic acid, gadoleic acid, erucic acid, brassidic acid. Of course, the fatty acids with an odd number of carbon atoms are also usable, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, Heptadecanoic acid, nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, Heptacosanoic.

In the context of the present invention, the use of fatty acids of the formula XIII in the reaction mixture for the preparation of the esterquats is preferred, so that preferred portioned fabric softener is a reaction product of trialkanolamines with a mixture of fatty acids of the formula XIII,

R ¹ -CO-OH (XIII)

in which R ¹ -CO- represents an aliphatic, linear or branched acyl radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds and dicarboxylic acids in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which was optionally alkoxylated and then quaternized in a manner known per se, contained in the compositions in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight.

Suitable dicarboxylic acids which are suitable for producing the esterquats to be used in the agents according to the invention are, in particular, saturated or mono- or polyunsaturated αω-dicarboxylic acids. Examples include the saturated species oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic and dodecanoic acid, brassylic acid, tetra- and pentadecanoic acid, thapic acid as well as hepta-, octa- and nonadecanoic acid, eicosanoic acid and eicosanoic acid, eicosanoic acid and called phellogenic acid. Dicarboxylic acids which follow the general formula XXIII are preferably used in the reaction mixture, so that portioned agents according to the invention are preferred which are a reaction product of trialkanolamines with a mixture of fatty acids and dicarboxylic acids of the formula XIV,

HO-OC- [X] -CO-OH (XIV)

in which X represents an optionally hydroxyl-substituted alkylene group having 1 to 10 carbon atoms, in a molar ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1, which was optionally alkoxylated and then quaternized in a manner known per se, in quantities from 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight in the compositions.

Have among the multitude of esterquats that can be produced and used according to the invention those in which the alkanolamine treithanolamine and the dicarboxylic acid is adipic acid. Thus, are within the scope of the present invention Agents particularly preferred which are a reaction product of triethanolamine with a Mixture of fatty acids and adipic acid in a molar ratio of 1: 5 to 5: 1, preferably 1: 3 to 3: 1, which then quaternizes in a manner known per se in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30% by weight included in the funds.

Depending on whether they are used as textile detergents, Washing aids or fabric softeners can be formulated - also with additional benefits be equipped. For example, there are color transfer inhibitors Compositions, anti-gray formula agents, ironing agents, agents with special fragrance release, agent with improved dirt release or Prevention of pollution, antibacterial agents, UV protection agents, color refreshing agents, etc. can be formulated. Some examples are explained below:

Because textile fabrics, especially from rayon, rayon, cotton and their Mixtures that can be creased because the individual fibers prevent bending, Buckling. Pressing and squeezing across the grain are sensitive Agents according to the invention contain synthetic anti-crease agents. Which includes 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 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. are important substances from these groups for example benzalkonium chlorides, alkylarlyl sulfonates, halophenols and Phenol mercuric acetate, with the agents according to the invention also entirely on these Connections can be dispensed with.

To undesirable effects caused by oxygen and other oxidative processes caused changes to the agents and / or the treated textiles prevent the agents may contain antioxidants. To this connection class include, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines and 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 according to the invention. antistatic agents increase the surface conductivity and thus enable an improved drainage formed charges. External antistatic agents are usually substances with at least a hydrophilic molecular ligand and give a more or on the surfaces less hygroscopic film. These mostly surface-active antistatic agents can be in nitrogenous (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 the ironing of the treated textiles For example, silicone derivatives can be used in the agents 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 five Have 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 according to the invention can also contain UV absorbers which act on the treated textiles and improve the lightfastness of the fibers. Compounds that have these desired properties are, for example effective compounds and derivatives of Benzophenones with substituents in the 2- and / or 4-position. Furthermore, too substituted benzotriazoles, in the 3-position 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.

Other conceivable additives which are preferred in special embodiments are surfactants, which in particular the solubility of the water-soluble wall of the flexible, preferably elastic, hollow body or the compartmentalization device can influence, but also their wettability and foam formation during Can control dissolution, as well as foam inhibitors, but also bitter substances that a accidental swallowing of such hollow bodies or parts of such hollow bodies Can prevent children.

Fragrances are the detergent, detergent and / or Serving agent portions added to the overall aesthetic impression of the products improve and the consumer in addition to the technical performance (fabric softener result) to provide a sensorially typical and distinctive product. As Perfume oils or fragrances can be used single fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, Alcohols and hydrocarbons. Fragrance compounds are of the ester type for example benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, Benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and Benzyl salicylate. The ethers include, for example, benzyl ethyl ether. To the aldehydes count z. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lileal and Bourgeonal.

The ketones include the ionones, α-isomethyl ionone, and methyl cedryl ketone. To the Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol. The hydrocarbons mainly include terpenes such as limonene and Pinene. Mixtures of different odoriferous substances are preferably used are coordinated so that together they have an appealing fragrance produce. Such perfume oils can also contain natural fragrance mixtures, such as they are accessible from plant sources. Examples are pine, citrus, jasmine, Patchouli, rose or ylang-ylang oil. Nutmeg oil, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The fragrance content is usually in the range up to 2% by weight of the total Portion of detergent, cleaning agent or care product.

The fragrances can be used directly in the wash-active (s), cleaning-active (s) or care-active preparation (s) are incorporated; but it can also be advantageous to apply the fragrances to the carrier, which will adhere the perfume to the laundry intensify and through a slower fragrance release for long-lasting fragrance of Take care of textiles. Cyclodextrins, for example, have become such carrier materials proven. The cyclodextrin-perfume complexes can additionally with other Auxiliaries are coated.

The perfumes and fragrances can basically in each of the portions (washing active or cleaning-active or maintenance-active preparations) of the invention Detergent, cleaning agent or care agent portions can be included. Especially however, it is preferred that they be in a detergent in one for the post-wash cycle portion or detergent portion provided or in one Detergent, especially in a dish care product, in one for the Rinse or rinse cycle provided partial detergent portion, specially Part care product portion, are included. You must therefore according to the invention from one only under the conditions (especially the temperature) of the post-wash cycle or After-care water-soluble, in the conditions (especially in the Temperature) of the preceding wash cycles or rinse cycles water-insoluble Material of the flexible, preferably elastic, hollow body or Compartmenting device (s) may be included. This is according to the invention for example with a multiple compartments in a flexible, preferably elastic, hollow body detergent, cleaning agent or care agent Portion feasible.

The detergent, cleaning agent or care agent portions according to the invention contained in a flexible, preferably elastic, hollow body with and without Compartments one or more wash-active, cleaning-active and / or care-active Preparations in such quantities that they are suitable for washing, cleaning and / or Sufficient care process. It goes without saying that two units are dosed (Hollow body) under special conditions (heavily soiled, e.g. heavily greasy laundry; heavily soiled dishes) possible.

In a particularly preferred embodiment of the invention, one in one or several flexible, preferably elastic, hollow body (s) with at least one Compartment contained detergent, cleaning agent or care agent portion die at least one, preferably the plurality, washing-active, cleaning-active or care-active preparation (s) in one or more forms from the group powder, Granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, briquettes, solutions, Melts, gels, suspensions, dispersions, emulsions, foams and gases. Preferred are gels and most preferred are liquid washing, cleaning, and / or care products. The form of the in one or more compartments of the flexible, preferably elastic, hollow body containing washing-active, there is no limit to cleaning-active and / or care-active preparation, as long as the hollow body can be used in the intended manner. It is as An essential advantage of the invention is that the use of fluid phases in detergent, cleaning agent and / or care agent portions becomes possible and a detergent suitable for the administration of such fluid phases, Detergent and / or care portion is provided. So in the Compartments of a hollow body liquids or gels, gases or foams alone or together with solid components in one or more compartments closed and in use with those to be washed, cleaned or closed Caring objects are brought into contact. This creates a new freedom of Packaging of detergents, cleaning agents and care products achieved.

The detergent, cleaning agent or care agent portions disclosed here consist from an external hollow mold that contains one or more fillings. The Hollow form can be divided into several compartments by partitions, whereby several fillings within the same hollow body are separate from each other can. Besides the compatibility with the material of the fillings Hollow mold made no demands, so that both solid and liquid Have phases (systems) portioned.

The invention also relates to filled hollow bodies which only partially consist of one disintegrable under washing, cleaning or care conditions Hollow body (s) giving shape stability, blow molded material, while the other parts of the enclosure not necessarily flexible, preferably elastic, in defined above must be.

The detergent, cleaning and / or care agent portions according to the invention can preferably be used for the separation of incompatible active substances by dividing them into several separate areas. The table below gives a non-restrictive overview of possible active substances and their division into different compartments. It was also specified in which packaging the corresponding preparation is contained in compartment (A) or (B).

extrusion blow molding

It was based in an extruder plasticizable polymer mass (blow molding compound) on a water-soluble polymer thermoplastic in a tubular preform reshuffled. An open end of the tube was under thermal treatment closed. The preform was then inflated, the compressed air through a Was fed blow mandrel, which also the opening of the invention Blow molded body trained. The blow molded body was filled and demolded.

Compartments can be created, for example, by using predetermined ones Place the wall (s) of the still moldable blow molded body by appropriate Facilities in the blow mold, this with the formation of subdivisions, d. H. closed cavities, merges and liquid-tight, preferably through thermal treatment, connects. However, preforms can also be used, with separate cavities, which then form a blow molding with several Compartments are blow molded. But it can also have several hollow bodies with and can be combined without a compartment.

Coextrusionsblasen

In this special form of extrusion blow molding, the hollow bodies are made with and without Compartments made of several layers of material. The preform will generated by several extruders acting on a common tube tool, so that a preform with several layers is created which then becomes the hollow body is blow molded.

Injection stretch blow molding

In contrast to extrusion blow molding, the preform is produced by injection molding. After being transferred to a conditioning station, the preform which has not yet cooled down is turned into transferred a blowing tool and axially there by applying a mechanical force pre-stretched and inflated to the hollow body with high air pressure, so that a Stretching takes place.

The subject matter of the invention is explained in more detail with the aid of the following examples, these are not to be understood as limiting the state of the invention.

EXAMPLE 1

First, a 500 ml EURO bottle (one of the standard Henkel bottle shapes for for example liquid cleaner formulations) from a cold water-soluble PVA blend Texas Polymers, U.S.A., type "Vinex 2034" blown. The Melt Flow Index of the The thermoplastic material used is 6-8 according to the specification in the catalog (2.16 kg; 2300).

A "Bekum BM 201" blow molding machine was used, with one Extruder screw "S 531" (50 mm diameter; length-to-diameter ratio of 20) and an ovalized blow mold. The polymer pellets were at one Screw speed of 20 rpm is drawn in. The temperature profile in the extruder was increasing from feed to nozzle head (zone 1: 150 ° C; zones 2 + 3: 160 ° C; Flange: 170 ° C; Head: 182 ° C; Nozzle: 185 ° C). The cycle time was 10 seconds Bottle threads at the top of the article had to be cut using a hot cutter be separated.

The wall thicknesses of the bottles manufactured here are 0.2 mm im Circumference, 0.6 mm on the reinforced bottle bottom and 0.8 mm in the area of the Cylinder thread.

As an example, the bottle was filled with a low-water detergent composition (see table as follows).
Low-water detergent formulation [%] sodium 16.0 sodium tripolyphosphate 71.7 sodium 5.0 tetraacetylethylenediamine 1.25 benzotriazole 0.5 C12 fatty alcohol with 3 EO 1.25 dye 0.1 enzymes 3.0 Perfume 0.2 silicone oil 1.0

The PVA bottle was then filled with a PVA Screw cap lock (0.5 mm wall thickness between the thread pitches) sealed liquid-tight. The screw cap used was from one suitable PVA blend also from Texas Polymers, U.S.A., type "Vinex 2019" (MFI 26-30; 2.16 kg; 190.C), on a hydraulic screw injection molding machine from Fa. Arburg has been injection molded.

The bodies were subjected to mechanical stress tests, which are usually used for design of outer packaging, subjected to, and using a universal testing machine from Zwick, type 1425.

As PVA material is known for its water content with the relative humidity of the surrounding air is in balance, the reproducibility of the mechanical measurements increased by putting the manufactured item on overnight Standard climate of 23 ° C and 50% rel. Moisture were conditioned.

• - Verformungsarbeit w und Rückstellgeschwindigkeit v der unbefüllten Flasche bei einem Stauchweg von 22 mm entlang der kürzesten Achse
  (Flasche liegend; Eindrückversuch mit 8 mm-Rundstab; Kraft F₁ = 16 N):
  w = 0,17 Nm.
  v = 73 mm/min.
• - Verformungsarbeit w und Rückstellgeschwindigkeit v der befüllten Flasche bei einem Stauchweg von 22 mm entlang der kürzesten Achse
  (Flasche liegend; Eindrückversuch mit 8 mm-Rundstab; Kraft F₁ = 70 N):
  w = 0,67 Nm.
  v = 53 mm/min.
• - Stauchwiderstand nach DIN 55526.1 (befüllte Flasche stehend, Füllgrad ca. 90%):
  F_max = 82,5 N
• - Streckspannung R_S bei 66% Dehnung: 10,0 +/- 2,4 N/mm².

The measured values were as follows:

• - Deformation work w and return speed v of the unfilled bottle with a compression path of 22 mm along the shortest axis
  (Bottle lying down; push-in test with 8 mm round rod; force F ₁ = 16 N):
  w = 0.17 Nm.
  v = 73 mm / min.
• - Deformation w and return speed v of the filled bottle with a compression path of 22 mm along the shortest axis
  (Bottle lying down; push-in test with 8 mm round rod; force F ₁ = 70 N):
  w = 0.67 Nm.
  v = 53 mm / min.
• - Shrink resistance according to DIN 55526.1 (filled bottle upright, degree of filling approx. 90%):
  F _max = 82.5 N
• - yield stress R _S at 66% elongation: 10.0 +/- 2.4 N / mm ² .

EXAMPLE 2

A cold-water-soluble 50 ml Liquid detergent application in a PVA case with an example of 0.08 mm Wall thickness in-line as a finished article.

Alternatively, there were two geometrical tools with two different tools Shapes available, namely a ball with a 48 mm outer diameter and one elongated, rounded and flattened cushion shape (clear dimensions 45 mm × 60 mm, 25 mm high).

To do this, the parison extruded from the PVA blend was first inserted into the open one Blow mold advanced and the tubular preform by means of a cutting iron (Warm cutter) cut below the mold.

In a subsequent step, the mold was closed, which means that at the same time Bottom of the preform was thermally sealed via the clamping effect. By means of a integrated blowing and filling quill unit, in the neck area of the preform in the Tool introduced, the preform was pressed to the ball or. pillow-shaped die walls of the tool. Alternatively, here Due to the small-volume cavity of the preform, the mold can also be attached to the inside applied vacuum are drawn into this.

A volume precisely presented by means of a dosage, here 50 ml as an example, one low-water liquid detergent formulation (composition as follows) was now about the integrated blowing and filling sleeve unit in the thin-walled, spherical or pillow-shaped PVA cover, filled in.

Then the integrated blow and fill sleeve assembly was withdrawn from the tool and then the upper jaws of the tool were closed in such a way that the necessary sealing of the casing to a liquid-tight PVA container was carried out by means of thermal sealing.
Low-water liquid detergent formulation water 0.5-15% org. solvent to 100% anionic surfactants 15-30% nonionic surfactants 15-30% alcohol 0-5% Soap 10-25% complexing 0-5% thickener 0-5% enzymes - protease 0-5% - amylase 0-5% - cellulase 0-5% additions AL = L CB = 3> - perfume and color

The fully demolded, filled articles were like the ones in the example above on theirs Compression resistance mechanically tested, but here for the sake of simplicity Exchange of the liquid detergent formulation content for glycerin as for PVA preferred test medium was dispensed with.

The crushing resistance of such a complete liquid detergent application according to DIN 55526.1 (filled pillow standing upright) resulted as an example:
F _max = 430 N.

The release of the liquid detergent formulation from the articles was initially in Beaker test (500 ml water; 60 rpm stirrer) checked. This resulted in a The dissolved PVA casing emerges after approx. 18 min at 30 ° C, after approx. 8 min at 40 ° C, after approx. 2.5 min at 60 ° C and after approx. 2 min at 90 ° C.

On the other hand, the washing machine test (washing ball put into the drum) that apparently due to the mechanical load, along with laundry, a release of the liquid detergent filling within the first 3 to 4 minutes.

EXAMPLE 3

Using a double blow mandrel, 2-compartment articles were Double chamber bottles (with and also without vertically running pinch seam) made of PVA Blown extruded and cut off at the bottle neck using a hot cutter. These were in Connection filled by hand up to a little above the middle, namely on the a page with the low-water liquid detergent formulation mentioned above, on which other side with a fixed bleaching system based on percarbonate the "handle Megaperls "composition. Then the above protruding PVA envelope with Teflonized heat sealing jaws of a hand sealing device at a sealing temperature of 160 ° C welded liquid-tight and the protrusion punched out, so that an article with approx. 90 vol .-% degree of filling emerged.

Claims (56)

1. A method for producing a flexible, preferably elastic, water-soluble hollow body containing an agent, in particular a washing, care and / or cleaning agent, comprising the steps: a) preforming a preform from a blow molding compound based on a water-soluble polymer thermoplastic; b) blow molding the preform into a hollow body; c) filling the hollow body with at least one agent, preferably washing, care and / or cleaning agent; and d) liquid-tight sealing of the blow-molded hollow body; e) the blow-molded hollow body filled and / or unfilled with at least one agent or glycerol as the test agent a) has a yield stress of between ≥ 3 N / mm ² and ≤ 15 N / mm ² when stretching along its longest axis, and / or b) with a compression path of 22 mm vertically, centrally, in the direction of its shortest axis, a deformation work of between ≥ 0.05 Nm and ≤ 5 Nm occurs, and / or c) at a force F ₁ > 0.1 N and ≤ 500 N is deformable along a path s ₁ and returns in the direction of the original shape after the loss of force, and / or d) after the loss of a deformation force, a return speed v of between> 0.01 mm / min and ≤ 650 mm / min, and / or e) the modulus of elasticity of the hollow body wall of the flexible unfilled hollow body produced by means of blow molding or filled with agents to 80 80% by volume is 1 1 GNm ² , preferably 0,1 0.1 GNm ² , preferably 0,0 0.01 GNm ² , and / or f) a compression resistance F _max of between ≥ 20 N and ≤ 2000 N occurs in the case of a blow-molded hollow body filled with an average of 80% by volume. 2. A method for producing according to claim 1, characterized in that the Melt flow index of the blow molding material at 10 kg between 1 and 30, preferably between 5 and 15, particularly preferably between 8 and 12 and / or the Melt flow index (MFI) of the blow molding material at 2.16 kg between 4 and 40, preferably between 5 and 20, particularly preferably between 8 and 15. 3. A method for producing according to claim 1 or 2, characterized in that the flexible, water-soluble hollow body is integrally formed. 4. A method for producing according to one of the preceding claims, characterized in that a) in a first step, a preform is produced by extrusion and b) in a second step in a cycle of the hollow body, preferably by means of a pressurized gas, preferably compressed air, blown, preferably to the final hollow body geometry, and filled with the agent, sealed liquid-tight, and then removed from the mold. 5. A method of manufacturing according to any one of the preceding claims, characterized characterized in that the wall thicknesses of the hollow body in certain areas can be formed differently by changing the wall thickness of the preform, preferably along its vertical axis, correspondingly of different thicknesses, preferably by regulating the amount of thermoplastic material, preferably by means of an adjusting spindle when the preform is removed from the Extruder nozzle, forms. 6. A method for producing according to one of the preceding claims, characterized characterized in that the hollow body with areas different outer Circumference and constant wall thickness produces by the wall thicknesses of the Preform, preferably along its vertical axis, accordingly of different thicknesses, preferably by regulating the amount thermoplastic material by means of an adjusting spindle when the Preform from the extruder nozzle, forms. 7. A method of manufacturing according to any one of the preceding claims, characterized characterized in that the preform, the hollow body and / or the liquid-tight closed hollow body from one or more component (s), the one or multiple materials based on one or different water-soluble polymeric thermoplastics. 8. A method for manufacturing according to any one of the preceding claims, characterized characterized in that the preform, the hollow body and / or the liquid-tight closed hollow body is tubular, spherical or bubble-shaped, the spherical hollow body a shape factor (= shape factor) of> 0.8, preferably of> 0.82, preferably> 0.85, more preferably> 0.9 and particularly preferably of> 0.95. 9. A method for producing according to one of the preceding claims, characterized characterized in that the walls of the blow molded Hollow body and / or the compartments have a wall thickness of between 0.05-5 mm, preferably from between 0.06-2 mm, preferably from between 0.07-1.5 mm, more preferably from between 0.08-1.2 mm, more preferably from between 0.09-1 mm and most preferably between 0.1-0.6 mm. 10. The method for producing according to one of the preceding claims, characterized in that the flexible, unfilled or ≥ 80 vol .-% hollow body produced by means of blow molding by a force F ₁ ≤ 500 N along a path s ₁ = 22 mm , in particular by a force F ₁ 100 100 N along a path s ₁ = 22 mm, preferably by a force F ₁ 60 60 N along a path s ₁ = 22 mm, more preferably by a force F ₁ 40 40 N along a path s ₁ = 22 mm and even more preferably by a force F ₁ 20 20 N along a path s ₁ = 22 mm, vertically, centrally, in the direction of its shortest axis of the hollow body, is deformable. 11. A method for producing according to one of the preceding claims, characterized characterized in that the flexible, unfilled or made by blow molding ≥ 80 vol .-% hollow bodies filled with glycerin after the loss of force Reset speed v ≤ 1000 mm / min. in particular v ≤ 500, preferably v ≤ 100 mm / min. preferably v ≤ 50 mm / min. more preferably v ≤ 10 mm / min and particularly preferably v ≤ 1 mm / min. having. 12. The method for manufacturing according to one of the preceding claims, characterized in that for the deformation of the flexible, unfilled hollow body produced by means of blow molding, a deformation work w ≤ 1.0 Nm along a path s ₁ = 22 mm, preferably w ≤ 0.75 Nm along a path s ₁ = 22 mm and preferably w ≤ 0.50 Nm along a path s ₁ = 22 mm, vertically, centrally, in the direction of the shortest axis of the hollow body, is required, or in the case of a path filled with ≥ 80% by volume with glycerol Hollow body a work of deformation w ≤ 5.0 Nm along a path s ₁ = 22 mm, preferably w; 2.5 Nm along a path s ₁ = 22 mm, preferably w ≤ 1 Nm along a path s ₁ = 22 mm, more preferably w ≤ 0.75 Nm along a path s ₁ = 22 mm and in particular w ≤ 0.5 Nm along a path s ₁ = 22 mm. To determine the deformation work, the deformation force F acts vertically, centrally, in the direction of the shortest axis of the hollow body. 13. A method for producing according to one of the preceding claims, characterized characterized in that the compression resistance of the blow molded flexible, unfilled or at least 80% by volume with at least one agent or glycerin as a test medium filled hollow body 75 to 400 N, preferably from between 100 to 300 N and in particular from between 150 to 250 N. 14. A method for manufacturing according to any one of the preceding claims, characterized in that the flexible, unfilled or ≥ 80 vol.% Hollow body produced by blow molding is filled with at least one agent or glycerol as test agent by a force F ₁ ≤ 100 N along a path s ₁ = 22 mm is deformable and has a restoring speed v ≤ 100 mm / min after the loss of force. 15. The method for producing according to any one of the preceding claims, characterized in that the modulus of elasticity of the hollow body wall of an at least two-part flexible unfilled or filled with glycerol filled with glycerol to ≥ 80 vol.% Water-soluble hollow body, preferably with screw and / or tilt closure, ≥ 0.01 GNm ² , preferably ≥ 0.1 GNm ² , preferably ≥ 1 GNm ² . 16. A method for producing according to one of the preceding claims, characterized characterized that one arranged serial, parallel and / or concentrically Produces hollow bodies and / or compartments, preferably, but not exclusively by using at least one double and / or multiple and / or Coextrusion blow pin used. 17. A method for producing according to one of the preceding claims, characterized characterized in that the opening (s) of the hollow body after filling liquid-tight, preferably by material closure, preferably by means of thermal Treatment, particularly preferably by applying a melt blob, closes. 18. A method for producing according to one of the preceding claims, characterized characterized in that the opening or openings of the hollow body through thermal treatment, preferably by fusing the walls to the border the opening, especially by means of clamping jaws, liquid-tight closes. 19. A method for manufacturing according to any one of the preceding claims, characterized characterized in that the washing and / or cleaning agent as a detergent Substances includes anionic surfactants and / or nonionic surfactants. 20. A method for producing according to one of the preceding claims, characterized characterized in that the at least one agent, preferably washing and / or Detergents, containing water-soluble hollow bodies 2 to 40 compartments, preferably 2 to 4, more preferably 2 to 3 compartments. 21. A method for producing according to one of the preceding claims, characterized characterized in that the respective compartments of the water-soluble Hollow body with a different content and / or a different Composition of substances, preferably washing-active substances, filled. 22. A method for producing according to one of the preceding claims, characterized characterized in that the respective compartments of the water-soluble Hollow body filled from above and / or below. 23. A method for producing according to one of the preceding claims, characterized in that a) the anionic surfactant content of between 3% by weight - 40% by weight, and b) the nonionic surfactant content of between 15% by weight - 65% by weight, based on the total weight fraction of the washing and / or cleaning agent contained in the hollow body, the total content of anionic surfactant and nonionic surfactant being ≤ 100% by weight. 24. A method for producing according to one of the preceding claims, characterized characterized in that the washing and / or cleaning agent as a detergent Substances cationic surfactants, amphoteric surfactants, builder substances, Bleaching agents, bleach activators, bleach stabilizers, bleach catalysts, enzymes, Polymers, cobuilders, alkalizing agents, acidifying agents, Anti-redeposition agents, silver protection agents, colorants, optical brighteners, UV Protective substances, fabric softener and / or rinse aid includes. 25. A method for producing according to one of the preceding claims, characterized characterized in that the agent is selected from the group comprising Medicines, plant protection products, foodstuffs, detergents, cleaning agents, Care products, cosmetics, hair dyes, agrochemicals, fertilizers, building materials and / or adhesives. 26. A method for producing according to one of the preceding claims, characterized characterized in that at least one compartment containing enzyme is free of Bleach and / or at least one bleach containing compartment free of Is enzyme. 27. A method of manufacturing according to one of the preceding claims, characterized in that at least one hollow body region and / or compartment region with at least one outer surface of between 0.01 mm ² and 10 cm ^{2 is} produced by means of blow molding, the wall thickness of this surface being around to ensure a faster dissolution in an aqueous solution, less than the wall thickness of the adjacent surface. 28. A method for producing according to one of the preceding claims, characterized characterized in that the wall thickness of the hollow body and / or the Compartments by means of blow molding so that it forms in the hollow body and / or agents contained in the compartments, in particular washing and / or Detergent, in the aqueous application liquor within ≤ 5 min. preferably within ≤ 3 min. preferably within ≤ 1 min. partially or is released completely. 29. A method of manufacturing according to any one of the preceding claims, characterized characterized in that the wall thickness of the hollow body and / or the Compartments by means of blow molding so that the in at least one Hollow bodies and / or enzymes contained in at least one compartment in time at least partially or completely before that in or at least one other Compartment contained bleach released into the aqueous application liquor become. 30. A method for producing according to one of the preceding claims, characterized characterized in that the wall thickness of the hollow body and / or the Compartments by means of blow molding so that the in the hollow body and / or enzymes contained in at least one compartment at least partially over time or completely ≥ 60 s, preferably ≥ 120 s, more preferably ≥ 240 s and am most preferably ≥ 360 s before that in or at least one other Compartment contained bleach released into the aqueous application liquor become. 31. A method for producing according to one of the preceding claims, characterized characterized in that the internal volume of the blow molded Hollow body and / or the compartments between 0.5 ml and 2000 ml, preferably between 2 ml and 500 ml, more preferably between 5 and 250 ml preferably between 10 and 100 ml, more preferably between 20 and 75 ml and am most preferably between 40 and 50 ml. 32. A method of manufacturing according to any one of the preceding claims, characterized characterized in that the blow molded hollow body and / or in the compartments the detergent and / or cleaning agent in solid, liquid form Form and / or gel form, preferably in the form of particles, suspensions, Emulsions, homogeneous solutions, pastes and / or in the form of transparent Solutions, add. 33. A method for manufacturing according to any one of the preceding claims, characterized characterized in that the blow molded hollow body and / or the compartments a multi-phase agent, in particular washing and / or Detergent, preferably a temporary two or three Three-phase mixture, which forms separate phases when left standing by shaking temporarily in the form of an emulsion, suspension or dispersion can be reversibly converted into a phase. 34. A method for manufacturing according to any one of the preceding claims, characterized characterized in that the multi-phase agent, in particular washing and / or Detergent, comprising at least one aqueous and / or non-aqueous phase, preferably at least one non-aqueous phase being liquid or solid and particularly preferably at least one aqueous phase is in gel form. 35. A method of manufacturing according to any one of the preceding claims, characterized characterized in that the blow molding to form the hollow body and / or the water-soluble thermoplastic used in the compartments is selected from the Group comprising polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, Polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, starch and derivatives of aforementioned substances, and / or mixtures of the aforementioned polymers, wherein Polyvinyl alcohol is particularly preferred. 36. A method of manufacturing according to any one of the preceding claims, characterized characterized in that during blow molding to form the hollow body and / or the compartments used, water-soluble thermoplastics additionally Polymers selected from the group comprising acrylic acid-containing polymers, Polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, Polyethers and / or mixtures of the above polymers are added. 37. A method for producing according to one of the preceding claims, characterized characterized in that the blow molding to form the hollow body and / or of the compartments, water-soluble thermoplastic used a polyvinyl alcohol comprises, the 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%. 38. Process for the preparation according to one of the preceding claims, characterized in that the water-soluble thermoplastic used in the blow molding to form the hollow body and / or the compartments comprises a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 . 39. A method for manufacturing according to any one of the preceding claims, characterized characterized in that the blow molding compound called the thermoplastics in quantities of at least 50% by weight, preferably of at least 70% by weight, particularly preferably of at least 80% by weight and in particular of at least 90% by weight, each based on the weight of the blow molding compound. 40. Method of manufacture according to one of the preceding claims, characterized characterized in that the blow molding compound plasticizer in amounts of at least> 1% by weight, preferably ≥ 10% by weight, particularly preferably ≥ 20% by weight and in particular of ≥ 30 wt .-%, each based on the weight of the Blow molding compound, contains. 41. The method according to any one of the preceding claims, characterized in that the Has hollow body flange parts and by positive locking and / or material locking, preferably by welding, with at least one other hollow shape is connected and / or closed. 42. The method according to any one of the preceding claims, characterized in that the Hollow bodies and / or the compartments to 20 to 100%, preferably 30 to 99 %, particularly preferably 40 to 98% and in particular 50 to 95% of their Volume be filled with agents, especially detergents and / or cleaning agents. 43. The method according to any one of the preceding claims, characterized in that the hollow body and / or the compartments with at least one, preferably several, wash-active, cleaning-active, rinse-active, care-active, pharmaceutically active preparation (s) and / or with at least one Food, pesticides, fertilizers, hair treatment products, Personal care products, cosmetics, building material, wallpaper paste or adhesive in the form of Powder, granules, extrudates, pellets, beads, tablets, tabs, rings, blocks, Briquettes, solutions, melts, gels, suspensions, dispersions, emulsions, Foams and / or gases partially or completely fills. 44. The method according to any one of the preceding claims, characterized in that the Hollow body and / or at least one compartment transparent and / or is translucent. 45. The method according to any one of the preceding claims, characterized in that the Hollow body no sealed seam, no squeeze seam and / or no circumferential seam having. 46. The method according to any one of the preceding claims, characterized in that at least one wall of the hollow body and / or at least one wall forms at least one compartment in multiple layers. 47. The method according to any one of the preceding claims, characterized in that at least two layers of the wall of the hollow body and / or at least two Layers of at least one compartment designed so that an intermediate space is formed between the layers. 48. The method according to any one of the preceding claims, characterized in that by means of coextruding a preform with several layers, preferably 2 to 5, which is then blow molded into a hollow body in which at least one Wall of the hollow body and / or at least one wall at least of a compartment is multi-layered. 49. Containing agents, in particular washing, care and / or cleaning agents Hollow body according to one of the preceding claims. 50. Use of the hollow body according to one of the preceding claims for recording of agents, in particular washing, care and / or cleaning agents. 51. Use of the agent, in particular washing, care and / or cleaning agent, containing hollow body for treatment, healing, washing, care and / or Cleaning, especially for washing, rinsing and / or cleaning soft fabrics and / or hard surfaces. 52. Washing method, in particular method for machine washing in a commercially available washing machine, comprising the steps that one - At least one detergent portion of the detergent and / or cleaning agent-containing hollow body according to one of the preceding claims in the washing machine, in particular in the dispenser and / or washing drum, enters; - the desired washing conditions are set; and - When these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the wash-active preparation (s) of the detergent portion into the wash liquor so that it comes into contact with the items to be washed. 53. Cleaning procedure, comprising the steps that one - At least one detergent portion of the detergent and / or cleaning agent-containing hollow body according to one of the preceding claims in the cleaning liquor; - you set the desired cleaning conditions; and - When these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the cleaning-active preparation (s) of the detergent portion into the cleaning liquor so that it comes into contact with the items to be cleaned. 54. Rinsing method, in particular method for machine rinsing in a commercially available dishwasher, comprising the steps that - at least one detergent portion contained in the hollow body and / or compartments according to one of the preceding claims is introduced into the dishwasher, in particular into its washing-up chamber and / or into its washing compartment; - the desired rinsing conditions are set; and - When these conditions occur, the hollow body and / or the compartments opens in the aqueous environment and releases the active wash (s) of the detergent portion into the wash liquor so that it comes into contact with the items to be cleaned. 55. Hollow body producible according to one of the preceding method claims. 56. Hollow body producible according to one of the preceding method claims a means.