EP1735424B1 - Liquid-crystalline washing or cleaning agent containing a particulate bleaching agent - Google Patents

Description

The present patent application relates to structured liquid detergents or cleaners containing Peroxocarbonsäureteilchen.

In detergents and cleaners in liquid form, especially if they contain water but also if they are anhydrous, it may due to chemical incompatibility of the individual ingredients to negative interactions of these ingredients with each other and to decrease their activity and thus decrease the washing performance of the agent as a whole come, even if it is stored relatively short. This decrease in activity relates in principle to all detergent ingredients which carry out chemical reactions in the washing process in order to contribute to the washing result, in particular bleaches and enzymes, although surfactant or sequestering ingredients which are responsible for solution processes or complexing steps, especially in the presence of said chemically reactive ingredients in liquid, especially aqueous systems are not unlimited shelf life.

In order to solve this problem, it has been proposed on various occasions not to incorporate all ingredients desirable for a good washing or cleaning result into a liquid agent at the same time, but to provide the user of the composition with several components that he or she only shortly before or during washing. or should combine cleaning process and containing only compatible with each ingredients, which come together under the conditions of use used. The common dosing of several components is compared to dosing only a single liquid agent, however, often perceived by the user to be too expensive.

Imidoperoxycarboxylic acids are known as bleaching components in detergents and cleaners. However, the problem is their low storage stability, especially in liquid Formulations and at higher pH's. To solve this problem, proposals have already been made in the prior art.

This is how the European patent application describes EP 0 510 761 A1 Particles of 6-phthalimidoperoxihexanoic acid coated with a layer of wax having a melting point in the range of 40 ° C to 50 ° C. From these particles, the bleaching agent can therefore be released only at temperatures above the melting point.

The European patent application EP 0 653 485 A1 discloses capsule compositions in which 6-phthalimidoperoxihexanoic acid is present as a dispersion in oil.

From the international patent application WO 94/13776 A1 hydrous liquid bleaches are known which contain 0.5 to 15 wt .-% peroxycarboxylic acid and whose pH is above the PK _a value of the corresponding carboxylic acid and less than 6.0.

The European patent application EP 0 386 566 A1 discloses suspensions of solid peroxycarboxylic acids in aqueous solutions containing ethoxylates of long chain aliphatic alcohols with HLB values between 6 and 11.

From the international patent application WO 96/10073 A1 Non-aqueous liquid detergents are known which contain from 2% to 30% by weight of particulate peroxygen bleach having particle sizes of from 0.2 to 1000 μm and from 10% to 40% by weight of particulate anionic surfactant containing sulfated C ₈ to C ₂₀ alcohols and is free of alkylbenzenesulfonate anionic surfactants, suspended in 1 wt .-% to 60 wt .-% of 1 to 80 times ethoxyli C ₆ - to C ₁₆ alcohol and 1 wt .-% to 60 wt .-%. % non-aqueous low-polarity solvent.

The contribution in " 5th World Surfactants Congress CESIO 2000, Proceedings Volume 2, pp. 1244-1252 "discloses in its section 7 liquid agents containing phthalimidoperoxycaproic acid (PAP) and classified into 3 types there, namely clear isotropic solutions, structured compositions, and anhydrous systems the statement that PAP can not be incorporated into clear isotropic aqueous media because of its low water solubility, and the structured agents are said to require specific surfactant systems. Combinations of linear alkylbenzenesulfonate or secondary alkanesulfonate with fatty acids in the presence of high levels of electrolyte are suggested, or mixtures of two nonionic surfactants, because such agents exhibit viscosity changes and phase separation upon storage.

Moreover, the effect of bleach stabilization measures described in the prior art, especially when present in liquid agents, is not always sufficient. For longer storage times, despite the use of said stabilizers, a decomposition of the bleaching agent and consequently a loss of bleaching action and thus the detergency can be observed.

Following the above-mentioned desire of the consumer for the possibility of convenient dosing, also products in pre-portioned form have become established on the market and are also extensively described in the prior art. There are descriptions of washing, cleaning or care products in the form of compressed molded body, ie tablets, blocks, briquettes, rings and the like, as well as packaged in foil bags portions of solid and / or liquid detergents, cleaning or care products.

In the case of single-dose amounts of detergents or cleansers, which come in foil bags packed in the market, foil bags made of water-soluble film have prevailed. These make a tearing of the packaging by the consumer unnecessary. In this way, a convenient dosing of a single, for a washing or cleaning course sized portion by inserting the bag directly into the washing machine or dishwasher, especially in their Einspülkammer, or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or in the hand-washing or rinsing basin, possible. The foil bag surrounding the washing, cleaning agent or care product portion dissolves without residue on reaching a certain temperature. Also in bags of water-soluble film packaged detergents and cleaners are described in the art in large numbers. Thus, the German patent application discloses DE 198 31 703 a portioned detergent or cleaner preparation in a bag of water-soluble film, in particular in a bag of (optionally acetalized) polyvinyl alcohol (PVAL), wherein at least 70 wt .-% of the particles of the detergent or cleaning preparation particle sizes> 800 microns ,

The prior art discloses processes for preparing water-soluble capsules of polyvinyl alcohol or gelatin, which in principle offer the possibility of providing capsules with a high degree of filling. The methods are based on introducing the water-soluble polymer into a shaping cavity. The filling and sealing of the capsules takes place either synchronously or in successive steps, in which case the filling takes place through a small opening in the latter case. Processes in which the filling and sealing are parallel, for example, in the WO 97/35537 described. The filling of the capsules takes place by means of a filling wedge which is arranged above two mutually rotating drums which have ball half shells on their surface. The drums carry polymer bands that cover the ball half-shell cavities. At the positions where the polymer band of one drum coincides with the polymer tape of the opposite drum, a seal takes place. In parallel, the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelhalbschalenkavitäten.

A process for the preparation of water-soluble capsules, in which first the filling and then the sealing takes place, is in the international patent application WO 01/64421 disclosed. The manufacturing process is based on the so-called Bottle-Pack ^® method, as described for example in the German patent application DE 14 114 69 is described. In this case, a tubular preform is guided into a two-part cavity. The cavity is closed, with the lower tube section is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.

In a first object, which solves the problem of stability of peroxycarboxylic acids in liquid agents, the invention relates to a bleach-containing liquid detergent or cleaning agent, which more than 0 wt .-%, in particular at least 1 wt .-%, but not more contains 10% by weight, in particular not more than 5% by weight, of water and a particulate peroxocarboxylic acid and forms a lamellar liquid-crystalline phase without the ingress of water and is characterized in that it contains 20% by weight to 50% by weight of ether sulfate , 20 wt .-% to 50 wt .-% liquid at room temperature hydrocarbon and up to 50 wt .-% C ₁₂ -C ₁₈ fatty alcohol contains.

The term "without water access", which refers to the lamellar liquid-crystalline phase, is intended to mean that directly after preparation of the composition and storage under exclusion of water coming from the outside there is a lamellar-liquid crystalline phase and also remains. In the case of access of water from the ambient air, which can occur, for example, during storage under real conditions, for example, as a result of diffusion through the packaging material, the lamellar liquid-crystalline phase does not necessarily have to remain indefinitely long. Rather, it may at least partially convert to a hexagonal phase which, in some cases, even enhances the stability of the peroxycarboxylic acid.

Lamellar liquid crystalline agents are known in the art. By optionally partial replacement of the amounts of water used for their preparation by an aqueous composition, for example a dispersion which contains the peroxycarboxylic acid, one arrives at means according to the invention.

The liquid hydrocarbon at room temperature is especially paraffin oil, and the C ₁₂ -C ₁₈ fatty alcohol is especially stearyl alcohol. The amounts of water mentioned are preferably in a simple manner by the Use of commercially available hydrous qualities of the other ingredients mentioned incorporated into the funds. If desired, the water content may also be partially, preferably up to half its amount, replaced by water-miscible lower alcohols, for example methanol, propanol, glycerol and preferably ethanol.

Under an ether sulfate, the alkali metal and ammonium salts of sulfuric acid monoesters of alkoxylated, in particular with 1 to 6 moles of ethylene oxide ethoxylated, straight or branched C ₇ -C ₂₁ alcohols, such as 2-methyl branched C ₉ -C ₁₁ alcohols having an average of 3, 5 moles of ethylene oxide (EO) or C ₁₂ -C ₁₈ fatty alcohols with 1 to 4 EO, understood.

If desired, agents according to the invention may also comprise further ingredients, which in particular include dyes, fragrances, enzymes, and / or optical brighteners, by which the lamellar liquid-crystalline phase is not unreasonably impaired.

It is essential that the agents according to the invention contain a particulate peroxocarboxylic acid. Preferably, the peroxycarboxylic acid has a water solubility in the range between 50 and 800 ppm. Preference is given here to the use of 6-phthalimidoperoxohexanoic acid. 6-Phthalimidoperoxohexanoic acid is for example from the European patents EP 0 349 940 and EP 0 325 328 known. Their use in liquid washing or cleaning agents is for example in the European patent applications EP 0 442 549 . EP 0 477 190 . EP 0 484 095 or EP 1 010 750 or the international patent applications WO 00/27960 . WO 00/27971 or WO 00/29536 known. The peroxycarboxylic acid is preferably present in finely divided form, in particular with average diameters of less than 100 μm. Milling methods that can be used to achieve such particle sizes are, for example, in the international patent application WO 00/27969 or the German patent application DE 102 59 262 disclosed.

Compositions according to the invention can be filled in the usual way in containers provided for liquid detergents or cleaning agents, for example canisters or bottles, and dosed by the user from these. For the sake of as above described then facilitated dosage, however, they are preferably offered in suitable sachets of water-soluble material.

1. a) Bereitstellen mindestens einer Kavität,
2. b) Einführen eines wasserlöslichen polymeren Thermoplasts in die Kavität,
3. c) Einfüllen des Mittels in die mit Thermoplast gefüllte Kavität(en) und
4. d) Verschließen der durch die Schritte a) bis c) erhaltenen Portion.

A preferred further subject of the invention is therefore a water-soluble portion containing an agent as described according to the invention and prepared by a process comprising the steps

1. a) providing at least one cavity,
2. b) introducing a water-soluble polymeric thermoplastic into the cavity,
3. c) filling the agent in the thermoplastic filled cavity (s) and
4. d) closing the portion obtained by steps a) to c).

A preferred method for preparing the water-soluble portions is the Rotary-Die method, as described for example in the WO 97/35537 for the preparation of water-soluble capsules is described. The production of water-soluble portions is effected in that the liquid agent is injected via a metering device by means of a filling wedge locally between two bands of water-soluble polymeric thermoplastic, which are located on two mutually parallel rotatably mounted forming rollers having on their lateral surfaces all round hollow shapes whose shape corresponds to half a portion to be produced. The sealing takes place by pressure contact of the two foil strips. In a preferred embodiment, to improve the seal, at least one of the water-soluble film strips is dissolved with a solvent prior to the molding process. Further preferred is the heat-sealing of the two portion halves. For this purpose, the two forming rollers can advantageously serve as electrodes for the dielectric fusing of the films together. To facilitate the shaping process by injecting the liquid, a vacuum can advantageously be applied to the cavities. As a result, the injection pressure of the liquid can be reduced and thus the risk of contamination of the polymer material with liquid contents at the sealing positions is reduced. Advantageously, the molding rolls in

Area of the forming roll webs roughening on. The roughening of the forming roll webs increases the static friction for the film strips from which the portions are produced.

About the shape of the molds in the form rollers can be produced portions of otherwise arbitrary geometries having a mirror plane. Geometries such as spheres, eggs, cubes, figures are preferred in the context of this invention.

The metering device injects a precisely metered amount of the liquid agent into the forming water-soluble portion. It is particularly advantageous if the injection shock is followed by a return stroke of the metering device. It is thus a dripping or stringing of the agent, which in turn can lead to contamination of the water-soluble film in the sealing position, avoided.

A further preferred method for producing water-soluble portions is the blow molding process. By means of blow molding, it is possible to produce water-soluble, flexible, preferably elastic, hollow bodies which contain agents, in particular detergent, cleaning agent and / or care agent portions. The blow molding process, as well as the rotary die process in comparison to thermoforming and injection molding process on significant procedural advantages. The blow molding process and the rotary die process saves material because no pinch edges or other protruding or excess parts have to be removed from the produced hollow bodies.

1. (a) Urformen eines Vorformlings aus einer Blasformmasse basierend auf einem wasserlöslichen polymeren Thermoplast;
2. (b) Blasformen des Vorformlings in einer Kavität zu einem Hohlkörper;
3. (c) Füllen des Hohlkörpers mit dem Mittel und
4. (d) flüssigkeitsdichtes Verschließen der so geformten und befüllten Portion.

The preparation of a water-soluble portion containing an agent according to the invention by means of blow molding comprises the steps:

1. (a) forming a preform from a blow molding composition based on a water-soluble polymeric thermoplastic;
2. (b) blow molding the preform in a cavity into a hollow body;
3. (c) filling the hollow body with the agent and
4. (D) liquid-tight closure of the thus formed and filled portion.

• (a) in einem ersten Schritt mittels Extrudieren ein Vorformling, vorzugsweise in Form eines Schlauchstücks, 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 (entsprechend den Bemessungen der Kavität) und mit dem Mittel, insbesondere einem Wasch-, Pflege- und/oder Reinigungsmittel gefüllt, flüssigkeitsdicht verschlossen, sowie anschließend entformt wird.

Advantageously, the production takes place in such a way that

• (A) in a first step by means of extrusion, a preform, preferably in the form of a piece of tubing produces, and
• (B) in a second step in a working cycle of the hollow body, preferably by means of a pressurized gas, preferably compressed air, blown, preferably the final hollow body geometry (according to the dimensions of the cavity) and with the agent, in particular a washing, care and / or detergent filled, sealed liquid-tight, and then removed from the mold.

Suitable blow molding processes include extrusion blow molding, coextrusion blowing, injection stretch blow molding and dipping blowing.

The cavity can be constructed of multi-part Forrnteilen, but is preferably a two-part cavity. To separate the preform and / or to close the portions, a blade is used in a preferred embodiment, such as in US Pat WO 01/64421 described. Particularly preferred is the use of a vibrating cutter as explicitly set forth in U.S. Pat EP 0 924 047 disclosed.

The filling opening of the hollow body after filling can be further closed, preferably by material closure, preferably by means of thermal treatment, particularly preferably by placing a melted spot.

• i) bei einer Dehnung entlang seiner längsten Achse eine Streckspannung von zwischen ≥ 3 N/mm² und ≤ 15 N/mm², aufweist und/oder
• ii) 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
• iii) 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
• iv) nach Wegfall einer Verformungskrafteinwirkung eine Rückstellgeschwindigkeit v von zwischen > 0,01 mm/min und ≤ 650 mm/min aufweist, und/oder
• v) das Elastizitätsmodul der Hohlkörperwand der mittels Blasformung oder Rotary-Die-Verfahren hergestellten flexiblen Portion bei einem Füllgrad von ≥ 90 Vol.-% ≤ 1 GNm², vorzugsweise ≤ 0,1 GNm², bevorzugt ≤ 0,01 GNm² beträgt, und/oder
• vi) bei einem mit Mittel zu ≥ 90 Vol.-% gefüllten blasgeformten oder nach dem Rotary-Die-Verfahren hergestellten Hohlkörper ein Stauchwiderstand F _max von zwischen ≥ 20 N und ≤ 2000 N, auftritt.

The filling opening or openings of the hollow body can advantageously be sealed in a liquid-tight manner by thermal treatment, preferably by fusing the walls adjoining the opening, in particular by means of clamping jaws. The water-soluble filled portions according to the invention produced by blow molding or rotary die processes have, in advantageous embodiments, the following properties, such that:

• i) when stretched along its longest axis has a yield stress of between ≥ 3 N / mm ² and ≤ 15 N / mm ² , and / or
• (ii) a deformation work of between ≥ 0,05 Nm and ≤ 5 Nm occurs at a compression path of 22 mm vertically, centrally, in the direction of its shortest axis, and / or
• iii) at a force F ₁ > 0.1 N and ≤ 500 N along a path s _{1 is} deformable and returns to the original shape after the elimination of the force, and / or
• iv) after removal of a deformation force effect has a return speed v of between> 0.01 mm / min and ≤ 650 mm / min, and / or
• v) the modulus of elasticity of the hollow body wall of the flexible portion produced by blow molding or rotary die process at a filling level of ≥ 90% by volume ≤ 1 GNm ² , preferably ≤ 0.1 GNm ² , preferably ≤ 0.01 GNm ² , and or
• vi) occurs in a filled with an average of ≥ 90 vol .-% blow-molded or produced by the rotary die process, a compression resistance F _max of between ≥ 20 N and ≤ 2000 N.

The portions according to the invention dissolve completely or substantially completely in water, in which way the agents contained in the closed hollow body are released to the environment. For example, the water-soluble portions according to the invention can be used in an aqueous machine washing, cleaning or care process. Preference is given to the use of the hollow body according to the invention in commercial washing machines or dishwashers. A use of the portions of the invention in hand basins or in a bowl is also possible. Important for the release of the agent contained in the portion is an external surrounding this aqueous environment.

The size of the hollow body is in preferred Ausfühnmgsformen of the invention such that the hollow body in the dispensing compartment of a commercial washing machine or dishwasher, in the laundry running nets or bags o.ä. can be entered. Particularly preferred embodiments of the detergent, cleaning agent or care agent portions according to the invention do not exceed a length (longest axis) of 10 cm, while the sizes of the width and the height are significantly lower, for example 1 to 5 cm.

Flexible hollow bodies in the sense of this invention also include, in particular, elastic hollow bodies. The term "elastic hollow body" is understood to mean, in particular, that the moldings containing the compositions have an intrinsic dimensional stability which makes them capable of breaking and / or under normal conditions of manufacture, storage, transport and handling by the consumer Pressure-stable, non-coincident structure, wherein the filled, blow-molded, or rotationally molded hollow body has a yield stress of between ≥ 3 N / mm ² and ≤ 15 N / mm ² when stretched along its longest axis, and / or at an upsetting distance 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 at a force F ₁ > 0.1 and ≤ 500 N along a path s _{1 is} deformable and returns after elimination of the force in the direction of the original shape, or after elimination of the force of the original form full constantly or almost completely assumes, and / or after removal of a Vernnngskrafteinwirkung a return velocity v of between> 0.01 mm / min and ≤ 650 mm / min, and / or the modulus of elasticity of the hollow body wall of the blow-molding or rotary die method flexible with an average of ≥ 90% by volume, filled hollow body ≤ 1 GNm ² , preferably ≤ 0.1 GNm ² , preferably ≤ 0.01 GNm ² , and / or with one with medium, to ≥ 90% by volume filled blow-molded hollow body a compression resistance F _max of between ≥ 20 N and ≤ 2000 N, occurs. In preferred embodiments of the invention, even the flexible, preferably elastic, hollow body itself have sufficient intrinsic dimensional stability, since this is advantageous the mobility in machines in the manufacture of the hollow body and the filling during the production of the portions affects.

As mentioned above, the portions produced according to the invention should preferably be at least partially reversibly deformable (in the case of irreversible deformation, no return speed would be measurable). In preferred embodiments of the present invention, the deformation is completely reversible, i. Preference is given to portioned washing, rinsing or cleaning agents according to the invention in which the filled portion returns to its original shape after the loss of force has ceased.

The force F ₁ is dependent on the indentation depth, since the hollow body opposes increasing resistance to the penetrating body. First of all, for the present invention it is only important that the hollow body can be deformed at a force of 500 N or less. In preferred embodiments of the present invention, the data refer to forces of penetration depths of a round rod with 8 mm diameter, in particular of 10 mm diameter, preferably of 15 mm diameter, preferably of 20 mm 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 determined exactly. In the case of a force acting through a round rod with 8 mm diameter and a penetration depth of S ₁ = 22 mm, the deformation work in blow molded or rotary Die produced flexible, filled hollow body is well below the values of comparable rigid unfilled bodies in which a deformation work of at least> 5 Nm must be made.

Another size for characterizing particularly preferred portioned agents according to the invention is the compression resistance. This can be determined in the form of a force-displacement diagram with commercially available tablet testers. For the purposes of the present invention, a Zwick type 1425 universal testing machine was used.

The determination of the compression resistance is carried out according to DIN 55526 Part 1, characterized in that hollow body (= water-soluble portion) standing upright between the plates of a pressure tester is set and compressed, wherein the pressure force and the Plattenweg be recorded until the required compression resistance and Plattenweg be achieved or by critical deformation or leakage of the container failure occurs.

The printing press was set to a compression speed of 10 mm / min. Afterwards the test procedure was started. The force applied to the portion at a penetration of 22 mm [N] was printed on the connected printer. The crush strength is given in N. Here, portioned means containing hollow bodies according to the invention with and without compartments are preferred, which are characterized in that the compression resistance F _{max of} the portioned agent-containing hollow body (= the filled hollow body with and without compartments) 20 to 2000 N, preferably 50 to 1000 N, especially preferably 75 to 600 N, more preferably 100 to 500 N and in particular 150 to 400 N is. For test purposes, the hollow body produced by means of blow molding or rotary die process is filled to ≥ 90 vol .-% with agent.

The wall thicknesses of the hollow body can be produced in different ways by blow molding, by varying the wall thicknesses of the preform, preferably along its vertical axis, according to different thickness, preferably by regulating the amount of thermoplastic material, preferably by means of an adjusting spindle during application of the preform from the extruder die, formed.

The hollow body may be blow molded with regions of different outer circumference and uniform wall thickness by varying the wall thicknesses of the preform, preferably along its vertical axis, preferably by regulating the amount of thermoplastic material by means of an adjusting spindle during application of the preform from the extruder die. formed.

In this way, different geometrical configurations of the hollow body can be blown with and without compartments. In a single work cycle can blow so bottles, balls, Santa Claus, Easter bunnies or other figures, which can be filled with medium, then sealed and then removed from the mold.

It is particularly advantageous that the hollow body can emboss and / or decorate during blow molding in the blow mold. By appropriate design of the blow mold, a motive can be mirror-inverted transferred to the hollow body. In this way, the surface of the hollow body can be designed practically arbitrary. For example, information such as calibration marks, application instructions, danger symbols, brands, weight, amount of waste, expiry date, images, etc. can be applied to the hollow body.

The preform, the hollow body and / or the liquid-tight closed hollow body of one or more component (s), wherein the component comprises one or more materials based on one or different water-soluble polymeric thermoplastics exists.

The preform, the hollow body and / or the liquid-tight closed hollow body may be tubular, spherical or bubble-shaped. A spherical hollow body preferably has 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 can be precisely determined by modern particle-measuring techniques with digital image processing. A common method is, for example, the Camsizer® system from Retsch Technology or the KeSizer® from Kemira. These methods are based on that the hollow body or body are irradiated with a light source and the hollow body detected as projection surfaces, digitized and processed by computer technology. The determination of the surface curvature is carried out by an optical measuring method, in which the "shadow cast" of the hollow body to be examined is determined and converted into a corresponding shape factor. The underlying principle for determining the form factor was, for example, Gordon Rittenhouse in "A visual method of estimating two-dimensional sphericity" in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pp. 79-81 described. The measuring limits of this optical analysis method are 15 μm to 90 mm. Methods for determining the shape factor for larger particles are those skilled in the art known. These are usually based on the principles of the aforementioned methods.

The walls of the hollow body produced by blow molding or rotary die process normally have a wall thickness of between 0.05 to 5 mm, preferably of between 0.06 to 2 mm, preferably of between 0.07 to 1.5 mm, more preferably from 0.08 to 1.2 mm, more preferably from 0.09 to 1 mm, and most preferably from 0.1 to 0.6 mm.

The portions according to the invention have wall thicknesses of water-soluble polymer formed in such a way that the portion-containing agent is generally released partially or completely into the aqueous application liquor within ≦ 5 min, preferably within ≦ 3 min, preferably within ≦ 1 min ,

To determine the release time, the portions were added to 10 liters of agitated water, stirrer speed ≥ 60 rpm, the water being at 90 ° C, preferably at 60 ° C, more preferably at 40 ° C, even more preferably at 30 ° C and in particular preferably heated to 20 ° C. More preferably, the release time is determined directly in the aqueous application liquor of at least one commercially available washing and / or dishwashing machine.

The internal volume of the water-soluble portions according to the invention may 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 between 10 and 100 ml, even more preferably between 20 and 75 ml and most preferably between 40 and 50 ml.

The water-soluble polymeric thermoplastic used to form the hollow body and / or the compartments is preferably selected from the group consisting of polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, cellulose, starch and derivatives of the aforementioned substances, polyvinyl alcohol (PVA), acetalized polyvinyl alcohol and / or mixtures of the aforementioned polymers, with polyvinyl alcohol being particularly preferred.

The polyvinyl alcohols described above are commercially available, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and Clariant L648.

Further polyvinyl alcohols which are particularly suitable as material for the hollow bodies are shown in the following table: description Degree of hydrolysis [%] Molecular weight [kDa] Melting point [° C] Airvol ^® 205 88 15-27 230 Vinex ^® 2019 88 15-27 170 Vinex ^® 2144 88 44-65 205 Vinex ^® 1025 99 15-27 170 Vinex ^® 2025 88 25-45 192 Gohsefimer ^® 5407 30-28 23,600 100 Gohsefimer ^® LL02 41-51 17,700 100

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

The water-soluble thermoplastic used to prepare the portion according to the invention may additionally comprise 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.

It is preferred if the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

More preferably, the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol ^-1 , preferably 11,000 to 90,000 gmol ^-1 , more preferably 12,000 to 80,000 gmol ^-1 and especially 13,000 to 70,000 gmol ^-1 lies.

Further preferred is when the thermoplastics in amounts of at least 50 wt .-%, preferably of at least 70 wt .-%, more preferably of at least 80 wt .-% and in particular of at least 90 wt .-%, each based on the weight of the water-soluble polymeric thermoplastic.

It is advantageous if the melt flow index ( M elt F low I ndex) of the polymer thermoplastic during extrusion, measured in the first step at 10 kg stamping load, between 1 and 30, preferably between 5 and 15, more preferably between 8 and 12 and / or Melt flow index (MFI) of the blow molding composition, measured at 2.16 kg stamping load, between 4 and 40, preferably between 5 and 20, particularly preferably between 8 and 15. In the context of the present invention particularly suitable for blow molding polyvinyl alcohol types are medium to high viscosity and have, for example, MFI values of 6-8 (at 230 ° C, 2.16 kg surcharge, PVA blend manufacturer Texas Polymers "Vinex 2034" or "2144") or 9-11 (at 190 ° C, 10 kg load, PVA blend "TP Vinex 5030").

The polymeric thermoplastics may be plasticized to improve their machinability, i. Plasticizer, included. This may be advantageous in particular if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been chosen as the polymer material for the portion. Glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proved particularly suitable as plasticizing auxiliaries.

It is advantageous if the polymeric thermoplastics plasticizer in amounts of at least> 0 wt .-%, preferably of ≥ 10 wt .-%, more preferably of ≥ 20 wt .-% and in particular of ≥ 30 wt .-%, each based on the weight of the blow molding compound.

The flexible, preferably elastic, water-soluble portion may have flange portions and possibly connected and / or closed by positive engagement and / or material closure, preferably by welding with at least one other mold.

The portion according to the invention is particularly preferably transparent and / or translucent.

The portion according to the invention preferably has no seam, in particular no sigla seam, no squeeze seam and / or no groove, in particular flanged groove.

In a particular embodiment of the invention, it is also possible that the walls of the flexible, preferably elastic, hollow bodies containing the detergent, cleaning agent or care agent portions, consist of different materials, so have a heterogeneous structure. For example, in a polymer material forming the wall of the hollow body, islands could be dispersed from a foreign material insoluble in the polymer, for example from another polymer (having different water solubility) or even from a completely different substance (for example, an inorganic or organic substance). Examples of these 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 carboxymethylcellulose. Such a structure may be associated in particularly preferred embodiments of the invention with the advantage that the other substance dissolves faster in water than the polymer, which allows penetration of water into the hollow body and thereby contributes to the accelerated release of the components of the portion. Overall, the entire dimensionally stable hollow body is dissolved faster in such a packaging than a molded body made of a pure polymer material. Similarly, it is possible to form the walls of the hollow bodies from layers of two or more polymers, which in particularly preferred embodiments can be chosen so that they themselves in terms of their properties (stability, heat resistance, water solubility, gas barrier properties, etc.) optimally complement.

In a further, likewise preferred embodiment, it is advantageous in accordance with the invention if the flexible element (s), preferably elastic (s), hollow body comprises one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes , Polyesters and polyethers and mixtures thereof.

• 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, Trimethylammoniummethyhnethacrylatchlorid (TMAEMC), Methacrylat-amidopropyl-trimethylammoniumchlorid (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.

With particular advantage, one or more materials may be cited from the following illustrative but non-limiting list:

• Mixtures of 50 to 100% polyvinyl alcohol or poly (vinyl alcohol-co-vinyl acetate) having molecular weights in the range of 10,000 to 200,000 g / mol and acetate contents of 0 to 30 mol%; these may include processing additives such as plasticizers (glycerine, sorbitol, water, PEG, etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called "slip agents" (eg "Aerosil"), organic and inorganic pigments, Salts, blowing agents (citric acid-sodium bicarbonate mixtures);
• Acrylic acid-containing polymers, such as. Copolymers, terpolymers or tetrapolymers containing at least 20% of acrylic acid and having a molecular weight of from 5,000 to 500,000 g / mol; Particularly preferred comonomers are acrylates such as ethyl acrylate, methyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and their salts and their esters such as methyl methacrylate, ethyl methacrylate, trimethyl ammonium methacrylate chloride (TMAEMC), methacrylate amidopropyl trimethyl ammonium chloride (MAPTAC ). Other monomers such as acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone are also useful with advantage;
• Polyalkylene oxides, preferably polyethylene oxides having molecular weights of 600 to 100,000 g / mol and their by graft copolymerization with monomers such Vinyl acetate, acrylic acid and salts thereof and their esters, methacrylic acid and salts thereof and their esters, acrylamide, styrene, styrenesulfonate and vinylpyrrolidone-modified derivatives (for example: poly (ethylene glycol-graft-vinyl acetate).) The polyglycol content should be 5 to 100% by weight. The amount of grafting should be from 0 to 95% by weight, the latter may consist of one or more monomers, a grafting fraction of from 5 to 70% by weight being particularly preferred, the water solubility decreasing with the grafting portion;
• Polyvinylpyrrolidone (PVP) having a molecular weight of 2,500 to 750,000 g / mol;
• Polyacrylamide having a molecular weight of 5,000 to 5,000,000 g / mol;
• Polyethyloxazoline and polymethyloxazoline having a molecular weight of 5,000 to 100,000 g / mol;
• Polystyrenesulfonates 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, vinylpyrrolidone; 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, especially the reaction products of diisocyanates (eg TMXDI) with polyalkylene glycols, in particular polyethylene glycols of molecular weight 200 to 35,000, or with other difunctional alcohols to products with molecular weights of 2,000 to 100,000 g / mol;
• Polyesters having molecular weights of 4,000 to 100,000 g / mol, based on dicarboxylic acids (eg terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid etc.) and diols (eg polyethylene glycols, for example with molecular weights of 200 to 35,000 g / mol);
• Cellulose ethers / esters, eg, cellulose acetates, cellulose butyrates, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose, etc .;
• Polyvinyl methyl ether with molecular weights of 5,000 to 500,000 g / mol.

Claims (6)

1. Bleaching agent-containing, liquid detergent or cleansing composition that comprises more than 0 wt.%, but not more than 10 wt.% water and a particulate peroxycarboxylic acid and forms a lamellar liquid crystalline phase without water ingress, characterized in that it comprises 20 wt.% to 50 wt.% ether sulfate, 20 wt.% to 50 wt.% hydrocarbon that is liquid at room temperature, and up to 50 wt.% C₁₂-C₁₈ fatty alcohol.
2. Composition according to claim 1, characterized in that the peroxycarboxylic acid is in finely divided form, particularly with average diameters below 100 µm.
3. Composition according to claim 1 or 2, characterized in that the peroxycarboxylic acid has a solubility in water between 50 and 800 ppm.
4. Composition according to one of claims 1 to 3, characterized in that the peroxycarboxylic acid is 6-phthalimidoperoxyhexanoic acid.
5. Water-soluble portion, comprising a composition according to one of claims 1 to 4, manufactured according to a process including the steps

   a) providing at least one cavity

   b) inserting a water-soluble thermoplastic polymer into the cavity

   c) filling the cavity/cavities that are filled with the thermoplastic with the liquid composition and

   d) sealing the portion resulting from the steps (a) to (c).
6. Portion according to claim 5, characterized in that it comprises a water-soluble sheath of a material from the group comprising polyvinyl alcohol (PVA), acetalized polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, cellulose, starch and derivatives of these substances.