EP2091833A1 - Closure comprising a self-opening closure flap - Google Patents

Abstract

The invention relates to a closure for a container (3) that is filled with at least one flowable or bulk product (3). Said closure comprises a closure base (4), fastening means (5) for fastening the closure base (4) to the container (3), a closure flap (6), at least one elastic, product-carrying tube (7) that is connected to the product-filled container so as to communicate therewith. The closure is characterized in that the elastic, product-carrying tube (7) has a first end (8) which is fastened to the closure (1), and a second end (9) that is movable relative to the closure (1), the closure (1) comprises at least one sealing element (10) that acts upon the tube (7) in the closure position of the closure flap (6) in such a manner that a discharge of the product (2) from the tube (7) is disabled, the free end (9) of the elastic, product-carrying tube (7) rests against the closure flap (6), the elastic tube (7), in the closed position of the closure flap (6), acts upon the closure flap (6) with a force effected by the deformation of the tube (7), said force being dimensioned in terms of its direction and amount in such a manner that the closing flap (6) is displaced from the closed position to the product-discharging position when the closure flap (6) is released from the snap-in element (11).

Description

 Closure with self-opening flap

The invention relates to a closure with automatically opening closure flap, wherein the automatic opening of the closure flap is effected by an elastic, product-carrying tube.

State of the art

From the prior art a variety of different closures for dispensing different products is known. There is a constant need to make such closures easier and more convenient for the user.

Especially in the field of detergents and cleaners, there is a trend towards flowable preparations, as they often have significant advantages in terms of their cleaning performance over the comparable powdery, granular or tablet-like, solid alternatives, with an increased attention recently on the cleaning performance at low temperature -Cleaning or in cleaning operations with reduced water consumption is placed.

A generic closure is known for example from EP1427647B1. EP1427647B1 discloses a closure formed in particular for dispensing beverages with an elastic, product-carrying tube, one end of the tube being fixed in the closure. Furthermore, the closure has a closure cap hinged to the closure body which, in the closed position, squeezes the tube against a sealing element, so that a product delivery is prevented by the corresponding cross-sectional constriction of the tube. To open the closure, the cap must be unlocked and folded so that the tube is upright in its product dispensing position. This must be the Locking container to be fixed in one hand of the user, while the shutter is opened as described above with the other hand.

Furthermore, the closure known from EP1427647B1 is unsuitable for sealing a surfactant-containing product, such as something a detergent or cleaner for textiles, household goods, household surfaces, for human skin or hair from accidental leakage, especially in an over-head position.

Object of the invention

The object of the invention is therefore to overcome the disadvantages known from the prior art and to provide a cost-producible closure, which makes it possible to open the closure with one hand in a simple and convenient way.

The object is achieved by a closure having the features of claim 1 and a packaging having the features of claim 19.

Advantage of the closure according to the invention is that no separate spring element is required for the formation of the self-opening mechanism, since the product-carrying, elastic hose acts both for product delivery from the container and as a spring element. As a result, the self-opening function of the closure can be realized in a very cost-efficient manner.

flap

A closure flap in the sense of this application is a closure means arranged on the closure which serves alone or in conjunction with the closure for closing a product discharge opening. Thus, all the lid suitable for the closure according to the invention, closure caps, pins, plugs and the like are covered by the term flap.

In particular, the closure flap can be designed as an outer flap, inner flap or closing flap, flap lid, cam cover, bayonet closure lid, hinge lid, sliding lid, snap lid, clamping lid, screw cap, slip lid, overcap lid or the like.

It is particularly advantageous to form the closure flap fixedly but movably on the closure so that the closure flap does not unintentionally detach from the closure when the closure is opened.

With regard to a cost-effective production of the closure according to the invention, it is advantageous to form the closure flap in one piece on the closure, wherein it is particularly advantageous that the closure flap in this embodiment can be articulated on the closure. Although this makes it possible to realize a low-cost and simple solution, material fatigue can occur in the vicinity of the hinge line, which can lead to crack formation and complete detachment or to a changing coupling behavior, depending on the structural design.

Therefore, it is preferable that the shutter is movably connected to the shutter via a hinge. Due to the storage, the movement of the closure flap does not lead to any wear that is relevant for the life of the closure.

In order to fix the product leading and dispensing hose relative to the closure flap and to ensure a guidance of the loose end of the tube when the closure flap is opened automatically, means for fixing the tube are provided on the closure flap. hereby Furthermore, it is ensured that the product delivery point in the delivery position of the flap is reproducible and defined.

The means for fixing the hose to the closure flap comprise all material, force, and / or form-fitting fixing means which appear suitable for the person skilled in the art.

In particular, the hose may be glued to the closure flap. In order to allow a movement of the tube during the opening or closing of the closure flap, the fixing means may also be formed as a sleeve arranged on the closure flap, through which the tube is feasible and which at least partially encloses the tube.

To configure the product dispensing amounts from the closure, the closure flap may include means for narrowing the tube cross-section. In particular, in the delivery of two products different flow behavior, for example, from a two-chamber container, an adaptation or adjustment of the metering can be done by adjusting the respective tube cross-sections.

tube

The product delivery as well as the force necessary for the automatic opening of the closure is realized in the closure according to the invention by a product-carrying, elastic tube.

The deformation of the elastic tube as the closure closes creates a force against the deformation by the elastic tube and causes the tube to spring back to its original position when the force inducing the deformation is removed from the tube. It is particularly preferred to cause a deformation of the hose due to a bending load, wherein one end of the hose is fixed in the closure, while a directed force at the free end of the hose causes a deflection, up to a kinking of the hose. As a result, sufficiently large spring paths between a closing position and a delivery position of the closing flap can be realized.

In order to ensure a complete, automatic opening of the closure into its dispensing position, it is advantageous that the tube has a certain elastic bias in the dispensing position. This can be effected by forming an angle α greater than 5 ° between the longitudinal axis of the tube in the product delivery position of the closure flap and the longitudinal axis of the tube in the untensioned state of the tube.

The hose is preferably made of an elastic plastic material. In particular, the tube is made of a silicone material.

opening aid

The closure comprises an opening aid for releasing the latching connection between the closure flap and closure, so that upon actuation of the opening aid, the closure is automatically moved out of the closure position into the product dispensing position by the spring effect of the tube.

In one embodiment, the opening aid may be formed as a finger recess on the closure, wherein the finger recess represents a recess below the locking element, in which a finger is inserted in such that it can be moved under or behind the shutter to release the latching connection. stabilizing element

A stabilizing element in the sense of this application is a component which is movably designed on and opposite a closure and can be moved from a first position, in which the closure can not be stably positioned on a substantially horizontal surface, into a second position in such a way that in this second position of the stabilizing element, the closure can be positioned so as to be stably over head on a substantially horizontal surface such that in the over-head position of the container at least a part of the closure, in particular the closure head, and at least a part of the closure in the second Position stabilizing element form the base of the closure.

In one embodiment of the invention, the stabilizing element is designed as a bracket. The bow shape has the advantage of providing a comparatively elongated, linear support edge, which serves to support the closure in the overhead position.

The stabilizing element can be movable relative to the closure by means of a rotary movement, a linear movement or a combination thereof.

The stabilizing element may be pivotable, extendable, hinged, extendable, herausdrehbar, be arranged opposite the closure.

The stabilizing element may be formed as a flap, strap, stamp, cylinder or the like.

In its second position, the stabilizing element biases a traverse, which encloses the footing of the closure on a horizontal flat surface in the overhead position. The support points of the shutter on the horizontal plane in this case form the support points of the polygon, when the support point is substantially punctiform or the sides of the polygon, when the support point is substantially linear.

The polygon can be designed in particular as Dreieich, truncated cone, square, rectangle, trapezoid, parallelogram.

In order to be able to position the closure with the container stably in the overhead position, the projection of the center of gravity of the container arranged on the closure is perpendicular to the horizontal plane within the standing surface of the closure spanned by the traverse.

It is particularly preferred that the center of gravity of the container relative to the center of gravity of the support surface is slightly displaced in the direction of the support line formed by the bracket, whereby the stability of the closure with the container can be further increased.

In a further, particularly preferred embodiment of the invention, the closure flap is fixed in the closed position by the stabilizing element shaped as a pivotable bracket in the closed position. By this forced sealing in which the self-weight of the container is used to create a leak-tightness enhancing pressure on the closure flap, the closure can be stably positioned for an extended period of time in the upside-down position, conveniently even with viscous products To achieve a virtually complete emptying of the container without the bottle must be manually held in the upside down position. The generation of a density-enhancing pressure further has the advantage that unintentional creep of surfactant-containing preparations is prevented by the sealing elements of the closure. In a further preferred embodiment of the invention, the bracket and the flap are firmly connected. This has the advantage that the bracket is moved during the transfer of the flap from the delivery position to the closed position and is positioned in the closed position of the flap of the bracket in its overhead standing position. The shutter is thus automatically prepared with the shutter closed for positioning in the overhead position.

In order to improve the slip resistance of the closure on the horizontal plane, the stabilizing element and / or the support region of the closure may be provided with a non-slip material.

In order to realize an automatic movement of the stabilizing element from its first to the second position, the stabilizing element can be coupled with spring elements, which automatically transfer the stabilizing element into the second position when releasing the stabilizing element from the first position by means of the spring action.

container

A container in the sense of this application is a device which is intended to cover a preparation in such a way that it can be shipped, stored and / or sold.

The container usually has a bottom and a lateral surface, through which a volume for receiving a preparation is formed. Furthermore, the container regularly has an opening for dispensing the preparation from the container, wherein the opening can be closed by a closure, in particular by the closure according to the invention.

The container may in particular be selected from the group of bottles, containers, cans, boxes, bags, etc. The container is designed in particular as a multi-chamber container, preferably as a two-chamber bottle.

The multi-chamber container can be produced particularly inexpensively by being made in one piece. For this purpose, in particular extrusion blow molding in which the multi-chamber container made of plastic such as PE, PP, polyester, co-polyester, PVC, TPE or the like are suitable.

In order to prevent that by compressing only one chamber, the Wirkstofffluidabgabecharaktehstik the multi-chamber container is affected, the multi-chamber container is advantageously formed substantially dimensionally stable. This ensures that the delivery from the multichamber container is effected essentially solely by the force of gravity acting on the active substance fluids.

The chambers are designed as complete containers and only connected to one another via at least one, preferably exactly one connecting web formed between the chambers. The connecting web is preferably integrally formed on the mutually facing inner sides of the chambers, in particular formed, for example, in the blow molding process with the chambers simultaneously. It is particularly expedient if the connecting web is arranged approximately centrally and i.w. - if necessary intermittently - extends over the full length of the chambers.

It is recommended that the multi-chamber container made of a material. This has advantages in terms of manufacturing complexity, less expensive manufacturing equipment, dimensional accuracy in manufacturing and the avoidance of additional joining costs. Preferably, the multi-chamber container is formed from a plastic.

In special cases, however, it may be necessary to manufacture the chambers of the multichamber container from different materials, especially if an active fluid would attack the material of a chamber.

Typical total volumes of receptacles within the scope of liquid detergents are between 100 ml and 10,000 ml, preferably between 1,000 ml and 3,000 ml.

In the scope of the budget, for example, detergents or dishwashing detergents, the usual total volumes of receptacles between 50 ml and 10,000 ml, with a preferred range between 400 ml and 2000 ml.

Of course, the total volume of the multichamber container is application specific and dependent on the drug fluids and can be scaled accordingly by those skilled in the art.

The extrusion blow molding process is a convenient process for producing the multichamber container of the invention. With appropriate modification, in particular of the blow molding process, it may be possible for the chambers, which are made in one piece with one another, to have a different light permeability and / or a different coloration. In particular, it may be advisable, despite a one-piece design opaque a receptacle, the other receptacle transparent or run in several receptacles, the receptacle in different colors. It has been shown that some drug fluids are photosensitive. Other active substance fluids to be administered in conjunction with the respective active substance fluid are less sensitive to light. An opaque coloring of the receptacle provided for the more photosensitive active substance fluid eliminates problems here. However, the extrusion blown process, like other production methods, also permits the separate production of the individual chamber and the subsequent joining of the chamber to a multi-chamber container

Composition of the active substance fluids

With regard to two-phase and multi-phase cleaning agents, reference may be made to the following printed publications, the disclosure of which is hereby incorporated by reference: DE 198 11 387 A or WO 99/47634 A, DE 198 11 386 A and WO 99/47635 A, DE 198, respectively 59 774 A or WO 00/39270 A, DE 100 62 045 A or WO 02/48308 A, DE 100 60 096 A or WO 02/44314 A, DE 198 59 799 A or WO 00/39268 A, DE 198 59 808 A or WO 00/39267 A, DE 198 59 778 A or WO 00/39269 A, DE 199 36 727 A or WO 01/10996 A, DE 199 45 506 A or WO 01/21753 A, DE 199 45 503 A or WO 01/21755 A, DE 199 45 505 A and WO 01/21754 A and DE 101 37 047 A. For the application of detergents in particular, the multi-chamber container may comprise, for example, formulations in the chambers. as described in DE 102 15 602 A1 and DE 101 49 719 A1, the entire contents of which are hereby incorporated by reference.

In addition to the liquids, flowable solids, such as, for example, powders, granules or microcompactates, are also considered as flowable substances / substance mixtures in the context of the present application. The stated solids may be present in amorphous and / or crystalline and / or partially crystalline form. The particle size of these flowable solids is preferably in the range of 10 to 2000 microns, more preferably in the range of 20 to 1000 microns and in particular in the range of 50 to 500 microns. Particularly preferred are flowable solids in which at least 70 wt .-% of the particles, preferably at least 90 wt .-% of the particles have a particle size below 1000 microns, preferably below 800 microns, more preferably below 400 microns. In the flowable substances, which may preferably contain one or more of the non-aqueous solvents mentioned above, further active substances may preferably be selected from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, Hydrotropes, foam inhibitors, preservatives, Disintegrationshilfsitte, Antiredepositionsmittel, antimicrobial agents, germicides, fungicides, antioxidants, glass corrosion inhibitors, and corrosion inhibitors may be included.

The preparation is particularly preferably formed by two separate liquid cleaning agents A and B.

builders

The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

With particular preference crystalline layered silicates of general formula NaMSi _x θ2 _X + i ^■ y H ₂ O used, wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline visually oily silicates of the formula NaMSi _x O _{2x +} I ^■ y H ₂ O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ ^.xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Sh ₄ O ₂₉ ^.xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ Oi ₇ ^.xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ ^.xH ₂ O, makatite).

Particularly suitable for the purposes of the present invention are crystalline layer silicates with the formula NaMSi _x O _{2x +} I ^■ y H ₂ O, in which x stands for 2 h. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ ^.yH ₂ O as well as further in particular Na-SKS-5 Ca-Na ₂ Si ₂ O _5), Na-SKS-7 (.beta.-Na ₂ Si ₂ 0 _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ^■ H ₂ O ), Na-SKS-10 (NaHSi ₂ O ₅ ^■ 3 H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ 0 ₅₎ and Na-SKS-13 (NaHSi ₂ O _5), in particular but Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) is preferred.

The liquid cleaning agents A and / or B preferably contain a proportion by weight of the crystalline semifinished silicate of the formula NaMSi _x O _{2 × +} I ^· y H ₂ O from 0.1 to 20% by weight from 0.2 to 15% by weight. and in particular from 0.4 to 10 wt .-%, each based on the weight of the respective cleaning agent A or B, are included.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 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, which preferably delayed release and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle ,

Alternatively or in combination with the abovementioned amorphous sodium silicates, X-ray amorphous silicates are used whose silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to the conventional water glasses on. Especially preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

In the context of the present invention, it is preferred that these silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in the liquid detergent A and / or B in amounts of 2 to 40 wt .-%, preferably from 3 to 30 wt .-% and in particular from 5 to 25 wt .-%, each based on the weight of the respective cleaning agent A or B, are included.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

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

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ OiO (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ OiO (potassium tripolyphosphate). The nathium potassium tripolyphosphates are preferably used according to the invention. If phosphates are used as washing or cleaning substances in the liquid detergents A and / or B in the context of the present application, preferred combination products contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate), in amounts of 5 to 60 wt .-%, preferably from 15 to 45 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the respective cleaning agent A or B. , are included.

Organic cobuilders

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitro-triacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

The citric acid or salts of citric acid are used with particular preference as builder substance. Combination products, characterized in that the at least one of the cleaning agent A or B citric acid or a Citric acid and that the weight fraction of citric acid or of the salt of citric acid, based on the total weight of the cleaning agent, is between 0.2 and 12% by weight, preferably between 0.2 and 8% by weight and in particular between 0, 2 and 6 wt .-%, are preferred according to the invention.

Another particularly preferred builder substance is methylglycine diacid (MGDA).

Process according to the invention, characterized in that the cleaning agent contains methylglycinediacetic acid or a salt of methylglycinediacetic acid and that the proportion by weight of methylglycinediacetic acid or of the salt of methylglycinediacetic acid is preferably between 0.2 and 12% by weight, preferably between 0.2 and 8% by weight and in particular between 0.2 and 6 wt .-%, are preferred according to the invention.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document. Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The content of detergents or cleaners to (co) polymeric polycarboxylates is preferably 0.1 to 10 wt .-%, preferably 0.2 to 8 wt .-%, particularly preferably 0.4 to 6 wt .-% and in particular between 0.4 and 4 wt .-%.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives , Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 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. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. Ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably used in form of its sodium or magnesium salts. Also preferred in this connection are glycerol disuccinates and glyceryl trisuccinates.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

enzymes

As a further component, the composition used as a cleaning agent contains enzymes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples include the subtilisins BPN 'and Carlsberg and their advanced forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilases, but not the Subtilisins in the narrower sense enzymes thermitase, proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases), can be used according to the invention to increase the bleaching effect. Polyphenoloxidasen) can be used. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities. A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.

A protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Preferred agents according to the invention contain stabilizers for this purpose.

One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also, peptide aldehydes, that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable. Other enzyme stabilizers are aminoalcohols, such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to Ci _2, such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Certain organic acids used as builders are capable, as disclosed in WO 97/18287, of additionally stabilizing a contained enzyme.

Lower aliphatic alcohols, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation due to physical influences. Likewise, calcium and / or magnesium salts are used, such as calcium acetate or calcium formate.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors. Other polymeric stabilizers are linear Cs-Cis polyoxyalkylenes. Also, alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and, preferably, are capable of additionally increasing their performance. Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.

Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation; For example, sulfur-containing reducing agents are familiar. Other examples are sodium sulfite and reducing sugars. Particular preference is given to using combinatons of stabilizers, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.

Another agent used with particular preference for stabilizing the enzymatic preparations is potassium sulfate (K ₂ SO ₄ ).

As stated at the outset, the proportion by weight of the enzymes in the total weight of the liquid cleaning agent A is between 0.1 and 10% by weight. In particularly preferred combination products, the proportion by weight of the enzyme in the total weight of the cleaning agent A is between 0.2 and 9% by weight and in particular between 0.5 and 8% by weight.

Although the liquid detergent B may of course also contain enzymes, it is preferred that the enzyme content of the detergent B be less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight. and in particular less than 0.1 wt .-% is. Particularly preferred methods according to the invention are characterized in that the liquid cleaning agent B contains no enzymes.

Preferably, one or more enzymes and / or enzyme preparations, preferably solid or liquid protease preparations and / or amylase preparations are used. In a particularly preferred embodiment, the liquid cleaning agent A comprises a combination of protease and amylase preparations. solvent

As a further constituent, the cleaning agents A and / or B contain a solvent. In the simplest embodiment, this solvent is exclusively water.

Preferred organic solvents are derived, for example, from the groups of the monoalcohols, diols, triols or polyols, the ethers, esters and / or amides. Particular preference is given to organic solvents which are water-soluble, "water-soluble" solvents in the context of the present application being solvents which are completely miscible with water at room temperature, that is to say without a miscibility gap.

Organic solvents preferably originate from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the given concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycehn, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di ethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl 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.

The organic solvents from the group of the organic amines and / or the alkanolamines have proven to be particularly effective with regard to the cleaning performance and again with regard to the cleaning performance of bleachable soilings, in particular of tea stains. In particular, the primary and secondary alkylamines, the alkylene amines and mixtures of these organic amines are preferred as organic amines. The group of preferred primary alkylamines include monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and cyclohexylamine. The group of preferred secondary alkylamines includes in particular dimethylamine.

Preferred alkanolamines are in particular the primary, secondary and tertiary alkanolamines and mixtures thereof. Particularly preferred primary alkanolamines are monoethanolamine (2-aminoethanol, MEA), monoisopropanolamine, diethylethanolamine (2- (diethylamino) ethanol). Particularly preferred secondary alkanolamines are diethanolamine (2,2'-lminodiethanol, DEA, bis (2-hydroxyethyl) amine), N-methyl-diethanolamine, N-ethyl-diethanolamine. Diisopropanolamine and morpholine. Particularly preferred tertiary alkanolamines are triethanolamine and triisopropanolamine.

Particularly powerful process variants are characterized in that the liquid cleaning agent A and / or the liquid cleaning agent B contains a solvent from the group of organic solvents, wherein the organic solvent is preferably an organic amine and / or an alkanolamine, preferably ethanolamine is.

If the cleaning agents A and / or B further comprise water in addition to the organic amine, preference is given to those methods according to the invention in which the weight ratio of water to organic amine and / or alkanolamine in the cleaning agent A or B is more than 1: 1, preferably more than 2: 1 and in particular more than 5: 1.

Particularly preferred cleaning agents A and / or B contain, based on the total weight of the respective cleaning agent, between 0.1 and 10 wt .-%, preferably between 0.5 and 8 wt .-% and in particular between 1, 5 and 6 wt. % of an organic solvent from the group of organic amine and the alkanolamines. Particular preference is given to processes according to the invention in which the liquid cleaning agent B, based on the total weight of the cleaning agent B, has a weight fraction of an organic solvent from the group of the organic amine and the alkanolamines between 0.1 and 10% by weight, preferably between 0, 5 and 8 wt .-% and in particular between 1, 5 and 6 wt.%, While the weight fraction of organic solvent from the group of organic amines and alkanolamines in the liquid detergent A, based on the total weight of the cleaning agent A, preferred is less than 5 wt .-%, preferably less than 3 wt .-%, more preferably less than 1 wt.% And most preferably less than 0.1 wt .-%, and in particular no organic solvent from the group of organic amines and the alkanolamine is contained in the detergent A.

viscosity

With regard to their meterability, those cleaning agents which have a viscosity of more than 10,000 mPas, preferably more than 50,000 mPas and in particular more than 100,000 mPas, have proven advantageous.

Preparations in which the viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ^° C., spindle 3) of at least one of the cleaning agents A or B is between 200 and 10,000 mPas, preferably between 500 and 7,000 mPas and are therefore preferred according to the invention especially between 1000 and 4000 mPas. The viscosity (Brookfield viscometer LVT-II at 20 rpm and 20 ^° C., spindle 3) of particularly preferred detergents or cleaners is above 500 mPas, preferably above 1000 mPas and in particular above 2000 mPas.

To achieve the desired viscosity of the cleaning agents, these agents are preferably thickening agents, in particular thickeners from the group agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, Casein, carboxymethylcellulose, core flour ethers, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas added, it has proved to be particularly advantageous if the detergents the thickener in quantities between 0.1 and 8 wt .-%, preferably between 0.2 and 6 wt .-% and particularly preferably between 0.4 and 4 wt .-% based on the total weight of the cleaning agent.

Natural-derived polymers used as thickening agents in the present invention are, as described above, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.

Modified natural products come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers.

A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickening agents from these classes of compounds are widely available commercially and are sold for example under the trade name Acusol ^® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^®-GT-282 -S (alkyl polyglycol ethers, Akzo), DEUTEROL ^® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ^® -xg (anionic heteropolysaccharide based on ß-D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH) , deuteron ^® -XN (non-ionic polysaccharide Schoner GmbH), DICRYLAN ^® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride copolymer, Monsanto), thickener QR 1001 (polyurethane emulsion, 19-21% in water / diglyme, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylate copolymer dispersion, 25% in water, Stockhausen), SER-AD FX-1100 (hydrophobic urethane polymer, servo Delden), Shellflo ^® -S (high molecular weight polysaccharide, stabilized with formaldehyde, Shell), and Shellflo XA ^® (xanthan biopolymer, stabilized with formaldehyde, Shell) is.

bleach

Bleaching agents may furthermore be present in the cleaning agent according to the invention, but with regard to the bleach content of the cleaning agents A and B, it is possible to distinguish between two preferred variants.

In a first preferred embodiment, the bleach content of the liquid detergents A and B is low and is preferably less than 2% by weight. Surprisingly, a cleaning performance could be achieved by the process control according to the invention by the use of bleach-poor detergent, which is comparable to the cleaning performance bleach-containing Reinger. By dispensing with bleaching agents, however, it was possible at the same time to increase the reciprocal freedom with decreasing production costs.

It is particularly preferred that the bleach content of the cleaning agents A and B are each less than 2 wt .-%, preferably less than 1 wt .-%, preferably less than 0.5 wt .-% and in particular less than 0.1 wt. -% is. Particular preference is given to processes according to the invention in which the cleaning agents A and B contain no bleaching agents.

In a second preferred embodiment, the cleaning agents A and / or B contain bleaching agents in which the cleaning agent B has a Bleaching agent content between 0.1 and 15 wt .-%. It is further preferred that the bleach content of the cleaning agent B, in each case based on the total weight of the cleaning agent B, between 0.5 and 15 wt .-%, preferably between 2.0 and 15 wt .-%, particularly preferably between 3 and 12 wt .-% and in particular between 5 and 10 wt .-% is. The bleach content of the cleaning agent A in this embodiment is preferably less than 2% by weight, preferably less than 1% by weight, preferably less than 0.5% by weight and in particular less than 0.1% by weight. It is particularly preferred that the cleaning agent A does not contain any bleaching agents.

In addition to H2O2, the group of bleaching agents includes, for example, the compounds H ₂ O _{2 which} supply water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate. Further bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, Diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronate).

If the cleaning agents A and / or B contain bleaching agents, bleach activators are preferably additionally used in order to achieve an improved bleaching action when cleaning at temperatures of 60 ^° C. and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycol (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

R1 R2-N- (CH ₂₎ -CN X ^"

R3

in which R ¹ is -H, -CH _3, a C _2-24 -alkyl or -alkenyl radical, a substituted C _{2- 24} alkyl or alkenyl group having at least one substituent selected from the group - Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or Alkenylarylrest with a Ci _-24 - alkyl group, or for a substituted alkyl or Alkenylarylrest with a Ci ₂₄ alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ - CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion ,

Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ - CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ - CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred, wherein from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" in which X ^{" represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

As bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycol (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic acid anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2 , 5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium acetonitrile methylsulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

If, in addition to the nitrile quats, further bleach activators are to be used, preference is given to bleach activators from the group of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (US Pat. n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA).

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

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, especially Preferably, the cobalt (amnine) -Konnplexe used, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate.

The chlorine bleaches have proved to be particularly effective for use in a process according to the invention. The group of these bleaching agents include, for example, heterocyclic N-bromo and N-chloroamides such as thchlohsocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin also belong to the group of these bleaching agents.

Preparations in which the cleaning agent B contains 0.1 to 20% by weight of a chlorine bleach are preferred.

surfactants

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G the symbol is that which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

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

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 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

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein Ci _-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest.

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

Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, Ci2-1 ₄ alcohols containing 3 EO or 4 EO, n-alcohol with 7 EO, Ci3-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _2- i8-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci _2- i ₄ -alcohol with 3 EO and Ci2-18-alcohol with 5 EO. The specified degrees of ethoxylation represent statistical averages that may correspond to a particular product of an integer or a fractional number. Preferred Al koholethoxylate have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

With particular preference, therefore, ethoxylated nonionic surfactant selected from Cβ-20-monohydroxy alkanols or C ₆ - per ₂ o-fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide - ₂ o-alkyl phenols or Ci ₆ Mol of alcohol were used. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-2o-alcohol), preferably a cis-alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide. Of these, the so-called "narrow ranks ethoxylates" are particularly preferred.

With particular preference surfactants are further used which contain one or more Taigfettalkohole with 20 to 30 EO in combination with a silicone defoamer.

Particular preference is given to nonionic surfactants which have a melting point above room temperature. Nonionic surfactant (s) having a melting point above 20 ⁰ C, preferably above 25 ° C, more preferably between 25 and 60 ⁰ C and in particular between 26.6 and 43.3 ° C, is / are particularly preferred ,

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

Nonionic surfactants from the group of alkoxylated alcohols, more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-N iosurfactants are also used with particular preference.

The nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control. More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse 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 initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

In the context of the present invention, particularly preferred nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula

R i -O- (CH ₂ -CH ₂ -O) - (CH ₂ -CHO) - (CH ₂ -CH ₂ -O) _r (CH ₂ -CHO) -H

R2 R3

preferably, R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ represents alkyl or alkenyl; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently stand for integers from 1 to 6.

The preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. When native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another are values of 1 or 2.

In summary, particularly preferred are nonionic surfactants having a C 1-6 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Surfactants of the general formula

R ^{1 is} -CH (OH) CH ₂ O- (AO) w- (A'O) χ- (A "O) y- (A" O) _z -R ² ,

in which R ¹ and R ² independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C _2-4 o-alkyl- or Alkenyl radical; A, A ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ - CH (CHs) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention.

Preference is given in particular to those end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R ¹ O [CH ₂ CH ₂ O] _X, CH ₂ CH (OH) R ²

in addition to a radical R ¹ which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, where x is between 1 and 90, preferably between 40 and 80, and especially between 40 and 60.

Particularly preferred are surfactants of the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] χ [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² ,

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15.

Particular preference is furthermore given to those end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH ₂ O] χ [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from --CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another are values between 1 and 32, wherein nonionic surfactants with R ³ = -CH ₃ and values for x of 15 to 32 and y of 0.5 and 1.5 are most preferred.

Other 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 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x> 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _J OR ^{2 may 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, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. 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 may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when 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 may 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 selected here by way of example and may well be greater, with 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 zu

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

simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is 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 is} H and x assumes values of 6 to 15.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.

Of course, the aforementioned nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants. Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the abovementioned general formulas, but rather those Mixtures containing two, three, four or more nonionic surfactants which can be described by different of the aforementioned general formulas.

Inventive method, characterized in that the cleaning agent A further contains 0.2 to 10 wt .-%, preferably 0.4 to 7 wt .-% and in particular 0.6 to 4 wt .-% nonionic surfactants, are preferred.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

As cationic active substances, for example, cationic compounds of the following formulas can be used:

R1

Ri-N- (CH _{2) n} -T-R 2 (CH _{2) n} -T-R2

Ri R3-N- (CH ₂₎ -T-R2

R4

residential each R ¹ group is independently selected from _Ci-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.

The group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

"Cationic polymers" in the context of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazoliniumchlohd Copolymers, the quaternized polyvinyl alcohols or the polymers listed under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

Preferred washing or cleaning agents, in particular preferred automatic dishwashing agents, are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ⁴ radical ³ , R ^{4 is} independently selected from Hydrogen, derivatized hydroxy group, C 1.30 linear or branched alkyl groups, aryl, aryl substituted Ci _-30 linear or branched alkyl groups, polyalkoyxylierte alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized nitrogen atom or at least one amino group a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one of R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic group having at least one positive charge without charged nitrogen, is at least one quaternized N atom or at least one amino group having a positive charge.

In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

X ^"

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion selected from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH , -CH ₂ -CH ₂ -OH, - CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

H ₂ C = C H- (C H2) -N ⁺ (CH ₃ ) 2- (CH ₂ ) -CH = CH ₂ X ^"

in the case of X ^" = chloride also referred to as DADMAC (diallyldimethylammonium chloride).

Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

R1 HC = CR2-C (O) -NH- (CH ₂₎ - N ⁺ R3R4Rs

X ^" in the R ¹ , R ² , R ³ , R ⁴ and R ^{5 are} independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ - CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _{n is} H and x is an integer between 1 and 6.

For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula H ₂ C = C (CH ₃ ) -C (O) -NH- (CH ₂ ) _X -N ⁺ (CH ₃ ) ₃

X ^"

in the case of X ^" = chloride also referred to as MAPTAC (Methyacrylamidopropyl- trimethylammonium chloride).

According to the invention, preference is given to using polymers which contain diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.

The aforementioned amphoteric polymers have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates. Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.

Preferred employable amphoteric polymers are selected from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers containing alkylacrylamide / methylmethacrylic acid / alkylaminoalkylmethacrylate Copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.

Preferably usable zwitterionic polymers are selected from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the

Acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

Also preferred are amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers, methacrylamidoalkyl trialkyl ammonium chloride and dimethyl (diallyl) ammonium chlorohd.

Particularly preferred amphoteric polymers come from the group of Methacrylamidoalkyl- trialkylammonium chloride / DimethyKdiallyOammoniumchlohd / acrylic acid copolymers, the Methacryl- amidoalkyltrialkylammonium chloride / DimethyKdiallyOammoniumchlorid / methacrylic acid copolymers and the

Methacrylamidoalkylthalkylammoniumchlorid / DimethyKdiallyOammoniumchlohd / A alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts. Particularly preferred are amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / DimethyKdiallyOammoniumchlori d / acrylic acid copolymers, the

Methacrylamidopropylthmethylammoniumchlorid / DimethyKdiallyOammonium chlohd / acrylic acid copolymers and the Methacrylamidopropyltrimethylammonium chlohd / dimethyl (diallyl) ammonium chlohd / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts. In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

Coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;

The encapsulation of the polymers by means of water-insoluble, meltable coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ^° C.;

The co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of washing- or cleaning-active substances, particularly preferably from the group of builders or cobuilders.

Preferred cleaning agents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of between 0.01 and 8% by weight, based in each case on the total weight of the combination product. Within the scope of the present application, however, preference is given to those combination products in which the weight fraction of the cationic and / or amphoteric polymers is between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, more preferably between 0 and 01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the cleaning agent is.

Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.

Particularly preferred as sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids containing sulfonic acid groups Monomers and optionally further ionic or nonionic monomers.

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

R ¹ (R ² ) C = C (R ³ ) COOH

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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula 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) is preferred.

In the sulfonic acid-containing monomers are those of the formula

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H

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, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional existing 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 ) -.

Preferred among these monomers are those of the formulas

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH 3) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H

in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , - CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = O 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, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said acids.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H. In summary, copolymers of i) unsaturated carboxylic acids of the formula R ¹ (R ² ) C =C (R ³ ) COOH in the 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 is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, ii) sulfonic acid group-containing monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in the 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 is -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = O 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 ) - iii) optionally further ionic or nonionic monomers particularly preferred.

Further particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid i) one or more sulfonic acid group-containing monomers of the formulas:

H ₂ C = CH-X-SO ₃ H

H ₂ C = C (CH ₃ ) -X-SO ₃ H

HO ₃ SX (R ⁶⁾ C = C (R ⁷⁾ -X-SO ₃ H in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , - CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional 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 ) - iii) optionally further ionogenic or non-ionogenic monomers.

The copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii). Particularly preferred polymers have certain structural units, which are described below.

For example, copolymers which are structural units of the formula are preferred

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

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein 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 ) - are, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the sulfonic acid-containing acrylic acid isocyanate is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein 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.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula

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

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C _O H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, as preferred as copolymers, the structural units of the formula

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

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C _O H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred. Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula

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

in which m and p are in each case an integer from 1 to 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein 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. Also preferred according to the invention are copolymers which contain structural units of the formula

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

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein 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.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas

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

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

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

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH 2 -CHC (O ) -Y-SO ₃ H] p- - [HOOCCH-CHCOOHl _m -tCHs-CCCHsJCCOJO-Y-SOsHlp-

in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein 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 ) - are, are preferred.

In the polymers, the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions. The use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.

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

In the case of terpolymers, particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^"1 , preferably from 4000 to 25,000 gmol ^{" 1} and in particular from 5000 to 15,000 gmol ^"1 . Combination products, characterized in that the cleaning agent A and / or the cleaning agent B further based on the total weight of the cleaning agent A or B 0.01 to 15 wt .-%, preferably 0.02 to 12% by weight and in particular 0, 1 to 8 wt .-% of one or more washing or cleaning active polymers, are preferred according to the invention.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the

Group of magnesium and / or zinc salts and / or magnesium and / or

Zinc complexes.

The spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ⁰ C. water temperature). The first group of zinc salts includes, for example, the zinc nitrate, the zinc oleate and the zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.

With particular preference is used as a glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or Zinkeitrat used. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred. Also suitable for glass corrosion protection are the soluble inorganic zinc salts, in particular the zinc sulfate, zinc nitrate and zinc chloride.

corrosion inhibitors

Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of the thazoles, the benzothazoles, the bisbenzothazoles, the aminothiazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. According to the invention, preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances preferably being present in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used. Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Especially effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1, 2,4-triazoles and mixtures of these substances.

In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds are used. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts, which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the Cobalt (amnine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, chlorides of cobalt or manganese, and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

Instead of or in addition to the silver protectants described above, for example the benzothazoles, redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation include all conventional mono-, di-, or tri-negatively charged inorganic anions, e.g. Oxide, sulfate, nitrate, fluoride, but also organic anions such as e.g. Stearate.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [I-hydroxyethane-1, 1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes selected from the group consisting of MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [I-hydroxyethane-1, 1 diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₂ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference.

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, ie completely coated with a waterproof material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage. Preferred coating materials, which by known methods, such as Sandwik melt coating processes from the food industry are applied to paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.

fragrances

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "body note" ) and "base note" (end note or dry out). Since odor perception is also largely based on the odor intensity, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances is therefore on the Odor impression and whether the corresponding fragrance is perceived as the head or middle note, nothing said.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

dyes

Preferred dyes, the selection of which presents no difficulty for the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic crockery do not stain them.

When choosing the colorant, it must be remembered that the colorants have a high storage stability and insensitivity to light as well as not too strong affinity for glass, ceramic or plastic dishes. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, colorant concentrations in the range of a few 10 ^-2 to 10 ^-3 wt% are typically selected. On the other hand, in the case of the pigment dyes preferred in particular because of their brilliance, but less readily water-soluble, the suitable concentration of the colorant in detergents or cleaners is typically from about 10 ^-3 to 10 ^-4 % by weight. Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.

preservative

The detergents of the invention may further contain preservatives. Preservatives from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable according to the invention such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides , Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1, 3-butanediol, phenoxyethanol, 1, 2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-Benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N - (3,4-dichlorophenyl) urea, N, N '- (1, 10-decanediyldi-1 -pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis ( 4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraazatetradecandiimidamide, antimicrobial quaternary surface active compounds, guanidines. However, particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones. In terms of their performance and storage stability, a number of cleaning agents have proven to be particularly advantageous:

The cleaning agents A and B designated by the serial numbers 33 to 64 preferably have a bleaching agent content below 2% by weight, preferably below 1% by weight, more preferably below 0.5% by weight and most preferably do not contain any bleaching agents. The closure according to the invention can be used in particular for dispensing washing and / or cleaning agents or personal care products such as shower gels, shampoos, body lotions or the like.

Further embodiments of the invention will be explained with reference to the accompanying drawings.

Show it:

1 Closure with closed closure flap in cross section FIG. 2 Closure with opened closure flap in cross section FIG. 3 Closure with opened closure flap in perspective view FIG. 4 Closure with opened closure flap on two chamber bottle in perspective view

LIST OF REFERENCE NUMBERS

1st closure

2nd product

3. container

4. closure body

5. Fasteners

6th flap

7. hose

8. first hose end

9. second hose end

10. sealing element

11. locking element

12. hinge

13. Pressure zone

14. slot

15th camp

16. Hose receptacle

17th stop element

18th pin

19. Hose fixation

20. Hose constrictor

21. recess

22. half shell-shaped depression

23. Rotary axis

24. half cup-shaped dome

25th plate

26. Stop

27. Procedure

28. Closure flap receptacle

29th Chamber

30th Chamber

31. Stabilizing element FIG. 1 shows the closure 1 according to the invention in a cross-sectional view. The closure 1 consists of a closure body 4 and the closure flap 6 is pivotally fixed.

The storage of the closure flap 6 in the closure base body 4 is realized by a hinge 12, as can be seen from FIG. 3 and FIG. The closure body 4 has around the axis of rotation 23 of the hinge 12 on a half-shell-shaped recess 22. The axis of rotation 23 of the hinge 12 and the central axis of the half-shell-shaped recess 22 are substantially congruent. The closure flap 6 has a half-shell-shaped dome 24 whose central axis is likewise congruent with the axis of rotation 23 of the hinge 12. The outer diameter of the mandrel 24 is slightly smaller than the inner diameter of the recess 22, so that the dome 24 can pivot into the recess 22 substantially without friction.

From the dome 24 extends a plate 25 to which a hose fixation 19 and hose constriction means 20 and a latching element 11 a are arranged. The dome 24 and the plate 25 are made in one piece and together form the closure flap 6.

On the closure body 4, a second locking element 11 b is arranged, in which the first, formed on the closure flap 6 locking element 11 a can engage, so that a locking connection between the closure flap 6 and closure body 4 is formed and the closure flap 6 releasably secured in a closed position in the closure body is.

An opening and a receptacle for a first hose end 8 of the hose 7 are provided in the half-shell-shaped recess 22 so that the hose end 8 communicates with the interior of a container to which the closure 1 is fixed in a liquid-tight manner. The opening is chosen smaller than the hose end diameter, so that the hose end 8 is shaped and / or can be placed non-positively in the opening. In addition, the hose end 8 may have shoulders that improve the fixation and tightness between the hose end 8 and the opening.

The second hose end 9 of the hose 7 is connected by a hose fixation 19 with the plate 25 of the closure flap 6. As can be seen from FIG. 3 and FIG. 4, the hose fixation is designed as a clamp in which the hose end 9 is fixed. It is possible, the hose end 9 alone or additionally cohesively, e.g. by gluing, to be attached to the plate 5. In the closed position of the closure flap 6 shown in FIG. 1, the tube 7 forms approximately a 90 ° angle between the first tube end 8 and the second tube end 9. Due to the elasticity of the tube 7, an upward spring force acting on the plate 25 is generated in this closure position, which is transmitted by the closure cap 6 as torque to the hinge 12. When releasing the latching connection 11a, 11b, the closure flap 6 is thus moved into a product dispensing position.

To release the locking connection, a pressure zone 13 is formed below the latching connection 11 on the closure base body 4, which causes a release of the latching connection when a pressure is exerted. The pressure zone 13 is defined by a pressure zone delimiting and U-shaped circumferential slot 14. The substantially U-shaped slot 14 is concave on the locking element 11.

The tab thus formed can be easily pushed by the user into the closure body 4 whereby the locking connection 11 b is moved on the closure body 4 by a lever action away from the closure body 4 to the outside, so that the locking connection 11a, 11b triggers and the shutter 6 automatically is moved to its dispensing position. For the exact definition of the product dispensing position, a stop 26 is arranged in the half-shell-shaped depression 22, against which the dome 24 of the closure flap abuts during a pivoting movement of the dome 24 and thus limits the opening angle of the closure flap 6.

In order to ensure a safe and complete opening of the closure flap 6, it is advantageous to arrange the stop 26 in such a way that when the closure flap 6 stops, the tube 7 has not yet been completely transferred into its unstretched original position. As shown in Figure 2, the first tube end 8 and the second tube end 9 form an angle less than 180 ° in the product dispensing position.

The closure base body 4 has a drain 27 below the hose end 9 fixed in the hose flap 6. Through the outlet 27, any product still leaking or dripping from the hose end 9 can be removed from the closure 1 so that visible product residues in the closure flap receptacle 28 of the closure body 4 are avoided.

In the plate 25 in the closed position of the closure flap 6 opposite region of the closure body 4, a sealing element 10 is arranged in such a way that it acts in the closed position of the closure flap 6 on the tube 7, so that a cross-sectional constriction of the tube 7 is effected. Preferably, the sealing element 10 is configured such that the tube 7 is tightly squeezed against accidental leakage of product. To improve the squeezing and to increase the sealing effect, a Schlauchverengungsmittel 20 may be disposed in the plate 25.

The tube constricting means 20 may further have the function to regulate the flow of product from the closure, in which it also in the product delivery position of the closure flap 6 a cross-sectional constriction of Hose causes and thus affects the flow characteristics of the product through the tube 7. In particular, for the delivery of two mutually different products which differ in their flow properties, a corresponding adjustment of preferred flow characteristics caused by tube narrowing means 20 may be advantageous. This is especially true for the setting of a defined metering ratio.

As can be seen from FIGS. 1-2 and 3-4, the closure 1 according to the invention can be designed both for the delivery of one or more, in particular two, products.

FIG. 4 shows the closure 1 according to the invention on a container 3 with two chambers 29, 30. The closure 1 is positively and non-positively fixed by bouncing on the container 3 liquid-tight. As can be seen in FIG. 4, the closure 1 is provided with a first product discharge opening 7a communicating with the first chamber 29 of the closure 1 and a second product discharge opening 7b communicating with the second chamber 30 of the closure 1, so that in the product delivery position of the container 3 product is discharged from the chambers 29,30 through the product discharge openings 7a, 7b to the environment.

The head of the closure 1 has a slope which drops from the stabilizing element 31 to the product discharge openings 7a, 7b.

On the closure 1, a stabilizing element 31 designed as a bracket is pivotably arranged, which can be pivoted from a first position applied to the closure 1 into a second, unfolded position. In this second position of the stabilizing element 31, the closure 1 with the container 3 can be positioned stably above the head on a substantially horizontal surface. In this over-head position of the container 3, a part of the closure 1 and the unfolded bracket 31 form the standing surface of the closure 1. The stabilizing element 31 is rotatably arranged in the hinge 12. The stabilizing element 31 has at the ends of the bracket in each case toward each other directed circular openings, which are positioned in alignment with the hinge axis. The hinge bearings are formed as circular openings, wherein the inner diameter of the bearings and the stirrup openings are approximately equal. The stabilizing element 31 is in the hinge bearings by a respective pin, which is feasible through the openings of the hinge bearing and the bracket 31, secured. The stabilizing element 31 may be equipped with a spring mechanism, which automatically moves the stabilizing element 31 in the over-head position when released from the closed position.

Of course, the invention is not limited to the illustrated embodiment. Further embodiments are possible without departing from the scope defined in the claims.

Claims

claims

A closure for a container (3) filled with at least one flowable or pourable product (2), comprising a. A closure body (4) b. Fastening means (5) for fixing the closure base body (4) on the container (3) in such a way that the closure (1) relative to the container (3) is sealed c. A closure flap (6) which permits from a first closure position in which the dispensing of product (2) from the closure (1) is prevented into a second product dispensing position in which dispensing product (2) from the closure (1) is, is movable, d. At least one elastic, product-carrying tube (7) communicating with the product-filled container communicating in such a way that product can be discharged from the container into the environment wherein i. The elastic, product-carrying tube (7) has a first end (8) which is fixed to the closure (1) and has a second end (9) that is movable relative to the closure (1) ii. The closure (1) comprises at least one sealing element (10), that in the closed position of the closure flap (6) acts on the tube (7) in such a way that dispensing of product (2) from the tube (7) is prevented. e. a locking element (11) that fixes the closure flap (6) in its closed position

characterized in that f. the free end (9) of the elastic, product-carrying tube (7) bears against the closure flap (6),

G. the elastic tube (7) in the closed position of the closure flap (6) counteracts a force of the closure flap (6) caused by the deformation of the tube (7), which is dimensioned with respect to direction and magnitude such that upon release of the closure flap (6) the latching element (11), the closure flap (6) is moved from the closed position into the product delivery position.

2. Closure according to claim 1, characterized in that the closure flap (6) is arranged articulated on the closure (1).

3. Closure according to claim 2, characterized in that the closure flap (6) is formed integrally with the closure (1).

4. Closure according to claim 1 or 2, characterized in that the closure flap (6) via a hinge (12) with the closure (1) is connected.

5. Closure according to one of the preceding claims, characterized in that the closure flap (6) comprises means for fixing the hose (7) on the closure flap (6).

6. Closure according to one of the preceding claims, characterized in that the closure flap (6) comprises means (20) for narrowing the tube cross-section.

7. Closure according to one of the preceding claims, characterized in that on the closure (1) an opening aid (13) for releasing the latching connection between the closure flap (6) and closure (1) is formed.

8. A closure according to claim 7, characterized in that a finger recess below the latching element (11) is formed.

9. A closure according to claim 7, characterized in that the closure (1) has a below the latching element (11) arranged pressure zone (13) which upon application of a predefined pressure force, releasing the latching connection between the closure flap (6) and closure (1 ) causes.

10. A closure according to claim 9, characterized in that the pressure zone (13) is at least partially bounded by a slot (14).

11.Verschluss according to claim 10, characterized in that the slot (14) is substantially U-shaped, facing the latching element (11) concave, is formed.

12. Closure according to one of the preceding claims, characterized in that the container (3) is formed as a multi-chamber container

13. Closure according to claim 12, characterized in that the closure (1) for each product (2a, 2b) containing chamber (29,30) each provides a separate tube (7a, 7b) which communicates with the respective chamber (29, 30) of the container (3) is communicatively connected.

14. A closure according to claim 13, characterized in that the hoses (7a, 7b) abut against a common closure flap (6).

15. Closure according to one of the preceding claims, characterized in that the hose (7) in the closed position of the closure flap (6) above the closure (1) fixed hose end (8) is bent.

16. Closure according to one of the preceding claims, characterized in that formed between the longitudinal axis of the hose (7) in the product delivery position of the closure flap (6) and the longitudinal axis of the hose (7) in the untensioned state of the hose an angle α greater than 5 ° is.

17. Closure according to one of the preceding claims, characterized in that the hose (7) is made of a substantially elastic plastic material.

18. Closure according to one of the preceding claims, characterized in that the hose (7) is made of a silicone.

19. Packaging comprising a. a container (3) for receiving a product b. a closure (1) disposed on the discharge opening of the container, characterized in that the closure is formed according to one of the features 1-18.

20. Packaging according to claim 19, characterized in that the container (3) is a multi-chamber container, in particular a two-chamber container.

21.Verpackung according to claim 20, characterized in that the

Chambers (29,30) contain mutually different preparations.

22. Packaging according to claim 21, characterized in that the preparations have mutually different viscosities.

23. Packaging according to one of claims 19 to 22, characterized in that the preparation or preparations comprises one or more substances from the group of bleaches, bleach activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, Dyes, Hydrotropes, Foam Inhibitors, Preservatives, Disintegration Aids, Anti Redeposition Agents, antimicrobial agents, germicides, fungicides, antioxidants, glass corrosion inhibitors or corrosion inhibitors.

24. Packaging according to claim 23, characterized in that the product has a surfactant concentration of at least 2 wt .-%.