DE10145618A1 - Portioned washing, rinsing or cleaning agents - Google Patents

Abstract

The invention relates to washing, dishwashing or cleaning agents that combine the advantages of liquid washing, dishwashing or cleaning agents such as good solubility and an esthetically pleasing look with those of solid forms, especially tablets. According to the invention, such agents are obtained by freezing into shape a washing, dishwashing or cleaning agent composition that is flowable at room temperature.

Description

The present invention relates to novel portioned washing, rinsing or cleaning agents, and Process for their preparation and their use.

Portioned detergents or cleaning agents are widely described in the prior art and have also prevailed in retail and consumers due to their advantages. As portioned Offer forms exist in the trade in powder or bags packed in bags made of water-soluble film Liquids and a variety of tablet-shaped detergents or cleaning agents.

The usual production of detergent tablets comprises the production Particulate premixes, the tableting process known to those skilled in the art into tablets be pressed. However, this method of production has significant disadvantages because it is sensitive to pressure Ingredients can be damaged during manufacture. So far, these ingredients such as B. encapsulated enzymes, etc. cannot be incorporated into tablets without loss of activity. In In some cases, instability or complete inactivity was to be expected. Also conditional the form of the compressed tablet that the ingredients are in close physical proximity stand in relation to one another, which leads to undesirable reactions in the case of incompatible substances, Instability, inactivity or loss of active substance. The strong compression also leads to this form of offer to reduce solubility. Generally there is a dichotomy between sufficient hardness (i.e. safe handling during packaging, transport and Application) and sufficiently fast disintegration and dissolution rates.

Solubility advantages can be expected when using liquid detergents or cleaning agents - with these Offer form, however, there are disadvantages in handling such as spilling, gluing on the measuring cup or bottle neck or a leak when dosing directly into the drum. Portioned liquid detergents or liquid detergents require a large technical Production effort and have because of the unstable bags and the associated space or leakage problems are only marginally accepted by consumers. In addition, a large part of the Manufacturing costs attributable to the elaborate packaging, so that the consumer for the the same amount of product pays more without getting more performance - the portioned Dosage must be "bought" by him, so to speak.

The present invention was based on the object of an offer form for washing, rinsing or To provide cleaning agents that can be metered in portions, but this portionability without one excessively increased manufacturing or packaging costs achieved. The advantages should be liquid detergent, dishwashing detergent or cleaning agent such as good solubility and high aesthetics with those more solid Offer forms, especially tablets, can be combined. In addition, one should greatest possible flexibility regarding the use of a wide variety of ingredients in which also unstable or incompatible raw materials without loss of activity May be part of the funds.

This task is accomplished by portioned washing, rinsing or cleaning agents with the characteristics of Claims 10 to 16 solved. In a first embodiment of the present invention, this relates to a manufacturing process for such moldings, namely a process for the production of portioned solid detergent, dishwashing detergent or cleaning agent, in which a detergent, The detergent or cleaning agent composition is frozen to give a shape.

The portioned washing, rinsing or cleaning agents produced by this process are distinguished on the one hand by the good solubility known from the liquid supply forms, since they melt and dissolve when the water enters, forming the application liquor. On the other hand, the portioned washing, rinsing or cleaning agents produced by this process have the same ease of handling as the tablets, microtabs, extrudates, etc. known from the prior art. In addition, the low temperature can also cause unstable ingredients, such as highly reactive peroxides , H ₂ O ₂ , peracids or other bleaching or oxidizing agents as well as labile ingredients such as enzymes can be incorporated safely and with a significantly reduced loss of activity.

The shaping freezing is carried out by cooling a washing machine which is flowable at room temperature, Detergent or detergent composition. In the context of the present invention 20 ° C, the term "flowable" denotes compositions that are capable are to be decanted by flow and thus includes liquids as well as more viscous gels or pastes. Flowable washing, preferably used in the context of the present invention Detergent or detergent compositions have viscosities at room temperature Range from 0.1 to 100,000 mPas, preferably from 0.5 to 20,000 mPas and in particular from 1 up to 5000 mPas. With regard to the ingredients of the flowable washing, rinsing or The detergent composition is not limited - it can be in the form of a Solution, dispersion or emulsion are present.

The term “freezing” or cooling process characterizes this in the context of the present invention Cooling down to values ≤ 0 ° C. In the context of the present invention, “frozen” is thus too understand that the temperature of the "frozen" is ≤ 0 ° C. This temperature is preferably even deeper, see below.

During the cooling process, the outer shape of the later portioned washing, rinsing or Detergent set. This can be done, for example, in a manner known per se by that a washing, rinsing or cleaning agent composition which is flowable at room temperature fills in molds and feeds the filled molds to a cooling unit. By choosing the right size and the shape of the shapes can directly influence the shape of the later portions become. The shapes can be chosen so that the consumer frozen portioned detergents, dishwashing detergents or cleaning agents can be given directly in the mold, the frozen portions can also be demolded and packed before sale. in the With regard to ecological and economic advantages (saving material for the molds) Processes according to the invention are preferred in which the washing, rinsing, flowable at room temperature or detergent composition poured into molds, frozen and then demolded becomes.

There are no limits to the expert's choice of casting molds, in addition to conventional ones Molds made of metals or plastics can also be used in molds similar to molding sand. Suitable release agents (e.g. starch or beeswax powder, pyrogenic Silicates, zeolites, finely divided carbonates etc.) spread out in bed and cut to the desired one Temperature cooled. Before, after or during the cooling process you can use a positive stamp Depressions are pressed into the bed, which form shapes after lifting the stamp. In these Wells can be washed, rinsed or flowable at room temperature Detergent composition can be metered in completely analogous to conventional forms. The shapes can then be separated from the moldings, for example by sieving. But it is also possible the powder matrix for the formation of a partial covering or the covering completely surrounding the molding to use. For this purpose, the moldings can be superficial after solidification in the powder matrix are thawed, causing the constituents of the powder matrix to be in direct contact with the molding are located, dissolved or glued to the molding. Through targeted variation of the Composition of the powder matrix can be caused by phenomena such as gelation or this process aqueous initiated setting are supported. Complete wrappings can be done this way when the moldings in the powder bed are covered with another powder layer become.

The demolded portions can subsequently be packed individually or in groups. Similar to that The frozen portioned washing, rinsing and washing can be delivered to private households with frozen food. or cleaning agents can then be delivered directly to the consumer, but it is also possible to deliver the portions to the retailer, who will then take them out of the freezer sold.

Alternatively, in the manufacture of the portioned washing, rinsing or cleaning agents the use of molds can be dispensed with, which can be particularly advantageous for smaller portions can. Here, methods are available with which the washing, rinsing or flowing at room temperature Detergents without an external shape are processed, for example by the Pelletizing, prilling, pastilling and scaling using chill rolls.

Alternative preferred methods are therefore characterized in that at room temperature flowable detergent, dishwashing or cleaning agent composition by incorporation into one Cooling flow is pelleted, prilled, pastilled or shingled.

The method of prilling involves the production of granular bodies from fusible materials, whereby In this variant of the method according to the invention, the washing, rinsing, flowable at room temperature or detergent composition at the top of a tower in a defined droplet size is sprayed, solidified in free fall by a stream of cold gas and the prills at the bottom of the tower accumulate as granules.

In general, all gases can be used as the cold gas stream, the temperature of the gas is below the freezing temperature. In order to avoid long falling stretches, is often with stronger cooled gases worked, for example with frozen air or even with liquid nitrogen, which is injected into the spray towers.

The grain size of the resulting prills can be varied via the choice of droplet size, whereby Particle sizes in the range of 0.5 to 2 mm, preferably around 1 mm, which are technically simple to implement lie.

An alternative method of twisting is pastilling. Pastilling includes that Dosage of the washing, rinsing or flowing at room temperature Detergent composition on rotating, inclined plates that are below the temperature Freezing temperature of the washing, rinsing or flowing at room temperature Have detergent composition. Process variants can also be carried out here where the pastilles are frozen. However, measures must be taken against this the condensation of humidity can be taken.

The pastillation provides larger particles, the sizes between 2 and Have 10 mm, preferably between 3 and 6 mm.

As an even more cost-effective variant for the production of particulate detergent components mentioned composition from flowable at room temperature washing, rinsing or The use of cooling rollers is ideal for cleaning agent compositions. Here, the at room temperature flowable detergent, dishwashing or cleaning agent compositions to a Cooling roller applied or sprayed on, the frozen portions scraped off and, if necessary crushed.

The use of cooling rollers enables the desired setting to be made without any problems Particle size range, which in this method according to the invention is also below 1 mm, for example at 200 to 700 microns.

The method according to the invention can be carried out with particular preference in such a way that pellets be produced with a spherical shape, preferably with a diameter of 0.5 to 5 mm, especially preferably have from 1 to 4 mm and in particular from 2 to 3 mm. For this are Preferred process variants according to the invention, in which the flowable at room temperature Detergent, dishwashing or cleaning agent composition in a cooling stream of a liquid coolant is introduced, at least frozen in the cooling stream to form pellets and then is removed from the cooling stream, the cooling stream preferably passing through as a horizontal cooling stream directed forced flow is generated in a coolant bath and particularly preferably for Generation of the cooling flow a liquid pump is used.

In this process variant, the washing, rinsing or flowing at room temperature Detergent composition, which is preferably a liquid to pasty mass, in one Cooling flow of a liquid coolant introduced, and in the cooling flow to form pellets at least frozen and then removed from the cooling stream. This can be done at room temperature flowable detergent, dishwashing or cleaning agent composition over a Drip device in an upwardly open, inclined gutter, in which a laminar flow out liquid nitrogen flows, be dropped. The drops are in the flow of nitrogen in a stream of nitrogen frozen to form pellets and then one of thermal insulation surrounding, perforated or grid-shaped conveyor belt fed. The flows through the openings liquid nitrogen, while the pellets in a gas channel through the exhaust air of the liquid Nitrogen completely frozen out on the conveyor belt and transported to a collecting container become.

The pellets are frozen in a stream of liquid nitrogen so that they have a certain Have minimum strength before they reach the conveyor belt. The resulting strength depends, among other things, on the dwell time of the pellets on the trough, and thus on their length from. To ensure that even with changing heat capacities and volumes of the washing, rinsing or detergent compositions sufficient pellet dwell times on the gutter To be able to ensure, the length is generous, so that the device is a relative has a large overall length.

An even simpler and cost-saving process variant for the reproducible production of Pellets which reduce the risk of deformation and which are used to carry out the Method suitable device is more compact, provides that the cooling flow is directed Forced flow is generated in a coolant bath.

In this variant of the method, the cooling stream is generated in a coolant bath. The pellets are frozen in whole or in part in the cooling flow. Mechanical contacts between the freezing pellets and a wall at a time when the pellets are not yet sufficiently hard and have strength are avoided. This will make them undesirable and not reproducible changes in the surface of pellets excluded.

A large cooling volume is available through the coolant bath. They freeze through the cold Pellets superficially and are thereby stabilized mechanically quickly. You can therefore in high pellet density and accordingly quickly from a dripping area in which they are in the Coolants are introduced, transported away without deformation or a Sticking through contact with one another is to be feared. The high pellet density allows one short cooling distance and thus a compact design of the device required for this. The Cooling flow is generated by directed forced flow of the coolant in the coolant bath. The Cooling flow, for example, is straight or circular within the coolant bath. With help In the directional flow, the pellets are between a defined feed point in which the Room temperature flowable detergent, dishwashing or cleaning agent composition into the cooling stream is introduced, and a defined removal point, in which the pellets are removed from the cooling stream are passed, so that the residence time of the pellets in the cooling stream can be set reproducibly can. Any fluctuations in the mass and density of the pellets, such as those that occur when the pellets sink freely or make them noticeable when buoyant in a coolant, are less important.

A horizontal cooling flow is preferably generated. A horizontal forced flow in the cooling bath is relatively easy to implement. In this regard, the generation in particular of a cooling flow through directed surface flow in the coolant bath has proven to be advantageous.

The use of a liquid pump has proven itself to generate the cooling flow. By means of the Liquid pump moves and moves liquid coolant in the coolant bath by suction and pressure thereby generating the cooling flow. The velocity of the forced flow is by means of Liquid pump variably adjustable.

A procedure has proven to be particularly favorable in which the pellets in the cooling stream frozen and discharged from the cooling flow by means of a conveyor and on the Conveyor are frozen out under the action of a gaseous coolant. Here are the pellets in the liquid cooling stream only frozen to the extent that they have no mechanical Impairment can be transported from the coolant bath.

The pellets are then completely removed by the action of a gaseous coolant frozen out, for which the cold exhaust air of the liquid coolant is particularly suitable. Under exhaust air understood the exhaust gas of the liquid coolant that forms during operation. By This procedure is used to completely freeze the pellets particularly cost-saving. In this case, a cooling stream is expedient, which is directed onto the conveying device is judged. Corresponding methods according to the invention, in which the pellets in the cooling stream frozen, discharged from the cooling stream by means of a conveyor and on the Conveyor are frozen out under the action of a gaseous coolant, wherein preferably the cold exhaust air of the liquid coolant is used as the gaseous coolant, are particularly preferred.

A further improvement of this procedure results from the fact that a cooling gas flow through directed forced flow is generated in the gaseous coolant, the cooling gas flow in parallel is guided to the conveying direction of the conveyor. The fact that the gaseous coolant to Example the exhaust air from the coolant bath in cocurrent or in countercurrent to the conveyor is moved, a defined and reproducible cooling of the pellets is achieved. The cooling gas flow is generated, for example, with the help of a gas extraction device.

When this method variant according to the invention is carried out, it becomes a commercially available one Immersion bath freezer with heat-insulating housing with a coolant bath made of liquid nitrogen surrounds. The coolant bath made of refrigerated nitrogen has a temperature of -196 ° C. through In a liquid pump, a directed cooling flow is generated in the coolant bath. By means of a Liquid pump is sucked in liquid nitrogen from the coolant suction opening, which comes from the Coolant outlet is discharged as a near-surface, horizontal cooling flow. Above the In the cooling stream, a dropping device is provided, by means of which liquid or pasty washing, rinsing or detergent compositions dropped into the cooling stream and entrained by it become. The detergent, dishwashing or cleaning agent composition that flows at room temperature is dripped into the cooling stream and moved with it to the transfer area. The middle Flow rate of the cooling stream on this route is around 0.2 m / s, and the Track length is about 100 cm. This results in an average residence time of the drops Beads from the detergent, dishwashing or cleaning agent composition in the liquid cooling stream of about 5. seconds. This treatment causes the beads to freeze to the surface, the mass of each with a diameter of about 6 mm is about 0.1 g. Because that Freezing in the coolant bath takes place very quickly and without any contact with walls, it is possible the beads from the detergent, dishwashing or cleaning agent composition with high Remove speed and density from the dropping area without mechanical There is a risk of damage to the beads.

Below the cooling flow and on a first section runs approximately parallel to it Conveyor belt, by means of the frozen beads from the washing, rinsing or Detergent composition are carried out of the coolant bath. For this, the Conveyor belt on a second section from the coolant bath diagonally upwards into one deducted channel-like outlet of the housing. The frozen pellets from the washing, Coolant flow carrying the detergent or cleaning agent composition is on the Upper area of the conveyor belt directed from the coolant bath. During this treatment evaporates part of the liquid nitrogen, which is used as exhaust air to completely freeze out the beads is used from the detergent, dishwashing or cleaning agent composition. this happens characterized in that in the transfer area of the conveyor belt from the coolant bath on the beads the conveyor belt, while the liquid nitrogen through openings in the belt in the Coolant bath drains away. While the beads from the washing, rinsing or Detergent composition on the conveyor belt through the channel-like outlet to the Collection containers are transported, they are completely frozen out in the exhaust air. To this The purpose of the exhaust air is above the conveyor belt in cocurrent with the direction of transport Detergent, dishwashing or detergent composition beads sucked in. The exhaust air is extracted while flowing through this distance the beads continue to receive energy and heat up there.

The belt length and speed of the conveyor belt are chosen so that the dwell time Beads from the detergent, dishwashing or cleaning agent composition on it for about 30 seconds is so that they are completely frozen at the end of the channel-like outlet.

In the channel-like outlet, the frozen spheres produced according to the invention are extracted from the Detergent, dishwashing or cleaning agent composition picked up by the conveyor belt and in transported a collection container.

Another option is the washing, rinsing or cleaning agents that are flowable at room temperature The corresponding compositions are to be processed without giving shape to the outside pre-cool so that pasty or gel-like masses result. These masses can then be Process in a manner known per se to shaped articles, for example by extrusion. This method also lends itself to the production of round particles by extruding pre-cooled masses, lumpy cut to length and then fed to a fillet. Because of the complex cooling of all Apparatus used in the manufacturing process can use the methods mentioned above depending on the desired particle shape and size, however, be more economical.

The pellets produced by the process according to the invention can in turn by means of a Cold chain are supplied to the retailer or the consumer who sells or uses them. It it is possible that the frozen detergent, dishwashing or cleaning agent composition is a complete washing, rinsing or cleaning agent with all the necessary components - however, it is also possible to add further components to the pellets produced according to the invention to mix, as is the case with conventional powder technology for washing, rinsing, or detergent is common. The beads produced according to the invention cannot only other beads of different composition produced according to the invention, but also particulate solids, granules, extrudates, flakes, etc. are added.

The inventive method has the advantage that the storage stability of the funds through reduced reactivity at low temperatures increases significantly. This can on the one hand considerable performance advantages for the consumer can be realized, on the other hand, too highly reactive ingredients are incorporated into the agents, which is not the case with conventional products or is only possible to a limited extent. For example, common liquid detergents only contain Exceptional bleaching, as bleaching agents are extremely unstable in aqueous liquid detergents. Non-aqueous bleach liquid detergents are expensive to manufacture and have, among other things Problems with settling stability. With the help of the method according to the invention conventional combination of bleach and bleach activator for the production of activated oxygen be dispensed with in the washing or cleaning liquor. Rather, the use of liquid bleaching agents and bleach activators or even frozen hydrogen peroxide possible, which is the possibility opened to further reduce the dosage in order to save packaging.

The agents produced according to the invention - regardless of whether they are larger, tablet-like objects or pellets or similar smaller objects - cooled processed or transported. However, the agents produced according to the invention can be used also encapsulate in a further process step, making an outer packaging unnecessary can. If the covering is chosen accordingly with regard to material and layer thickness, the Cold chain are also interrupted, and the consumer gets new in this way packaged liquid detergents, dishwashing detergents or cleaning agents on hand.

Process variants in which the frozen detergent, dishwashing or cleaning agent composition is then preferred in a subsequent process step.

The coating can be applied using known coating technologies. Here are particularly preferred processes in which the casing is melted by application Wrapping materials are carried out, with water-soluble wrapping materials being preferred. details Information on the type of wrapping materials and the composition of the wrapping can be found further down.

Processes according to the invention are independent of the type of wrapping materials used preferred in which the thickness of the sheath 0.1 to 500 microns, preferably 5 to 200 microns and is in particular 10 to 150 microns.

As already mentioned above, the frozen portioned washing, rinsing or Detergents can also be thawed easily after the wrapping process. So are Preferred processes are characterized in that the coated portioned washing, rinsing or detergent thawed before packing.

In contrast to conventional liquid washing, packed in pouches or bags or capsules, Detergents or cleaning agents have the end products of the process according to the invention according to Thawing a completely new structure. So bags always have and are sealed thus limited in shape. Other containers must be made with "bunghole" that is subsequently closed, a seam also being formed. Also procedures for Capsule production, in which seamless capsules with liquid filling can be produced do not exist. The method according to the invention enables the formation of a completely homogeneous coatings over the entire frozen molded body. Forms after thawing the wrapping is an ideal casing that contains the liquid washing, rinsing or washing inside Detergent wraps seamlessly and completely, so unlike everyone else known methods of packaging liquids no residual volume remains unused.

More detailed information on the composition of those that can be frozen using the method according to the invention Detergent, dishwashing or cleaning agent compositions, the type and amount of those contained in them Ingredients can be found below.

The process of encasing frozen compositions and subsequent thawing is not only applicable to detergents, dishwashing detergents or cleaning agents. Rather, it delivers Aspect of the present invention a novel, universal possibility for producing "packaged" Liquid products or capsules that have the advantages mentioned above. Another The present invention therefore relates to a process for producing portioned, liquid, encapsulated compositions, in which a composition flowable at room temperature frozen in shape, encased in a subsequent process step and after encasing is thawed. This method can be used universally for all compositions are flowable at room temperature and can be reversibly frozen to a solid. It is especially but not exclusively applicable to water or aqueous solutions. Areas of application are, for example, the production of liquid-filled portions Agrochemicals (fertilizers and pesticides, etc.), food ("solid" beverages, encapsulated food and nutritional additives etc.), animal feed, pharmaceuticals (capsules or "liquid tablets" etc.), colors and fragrances, or other industrial areas.

The coating can be applied to the frozen compositions using known methods Spraying, dipping, melting or veil coating techniques are used, with solutions from Coating materials can be used.

The method according to the invention provides novel, previously unknown in the prior art Products. Another object of the present invention is therefore a portioned solid Detergent, dishwashing detergent or cleaning agent that has a temperature below 0 ° C, preferably below -5 ° C, particularly preferably below -10 ° C, more preferably below -15 ° C and in particular below -18 ° C.

The temperature of the portioned solid washing, rinsing or washing according to the invention is down Theoretically, detergents are only limited by absolute zero. economic Considerations for the cold chain right up to retail / consumers leave it technically Easily achievable value of -196 ° C for liquid nitrogen or of -78 ° C for dry ice appear to be more manageable. With regard to the technical equipment of the consumer, who should be able to store the portions according to the invention at home until they are used Temperatures of preferred portions according to the invention at or above -30 ° C., for example at -29 ° C, -28 ° C, -27 ° C, -26 ° C, -25 ° C, -24 ° C, -23 ° C, -22 ° C, -21 ° C, -20 ° C or -19 ° C.

Washing, rinsing or cleaning agents preferred according to the invention are characterized in that it becomes fluid when the temperature rises to room temperature. It is particularly preferred that when the temperature rises to room temperature, the viscosities mentioned above are reached become.

The washing, rinsing or cleaning agents according to the invention are "portioned". That is, this a majority or a fraction of those required for a wash, rinse or cleaning cycle Dosing units include. According to the invention produced by means of molds, usually larger, Portions can include a metering unit and optically to the consumer known tablets may be based. Another preferred molded article to be produced can, comprises two, three or more dosing units and has a plate or plate-like Structure with alternately thick long and thin short segments, so that individual segments from this "bolt" at the predetermined breaking points, which represent the short thin segments, canceled and entered into the machine or application fleet. This principle The "bar-shaped" shaped body can also have other geometric shapes, for example vertically standing triangles, which are connected to each other only on one of their sides are to be realized. Appropriate portionable items are the consumer from the Confectionery industry ("Ritter Sport", "Toblerone") well known.

Of course, a portion according to the invention can also be a fraction of a metering unit include, so that the consumer not only one, but two, three, four or even ten to ten Portions can dose. This is the case, for example, with the beads produced according to the invention can be easily implemented.

Washing, rinsing or cleaning agents according to the invention are preferred here, the particle sizes of 0.5-10 mm, preferably from 1 to 7.5 mm and in particular from 1.5 to 5 mm.

Should detergents, dishwashing detergents or cleaning agents according to the invention be produced which count (jund should not be metered like a conventional powder), it is preferred that the Washing, rinsing or cleaning agents according to the invention 0.1 to 20 times, preferably that 0.25 to 10 times, particularly preferably 0.5 to 5 times and in particular one to three times Amount of dosage units required for a washing, rinsing or cleaning cycle.

As mentioned above, the washing, rinsing or cleaning agents according to the invention can be Also wrap servings. Corresponding washing, rinsing or cleaning agents according to the invention, the characterized in that they are encased are preferred according to the invention. Likewise It was mentioned above that the coated detergents, dishwashing detergents or cleaning agents The present invention can also be handled outside the cold chain, since the wrapping can be handled like a seamless, ideally filled packaging behaves. Here are washing, rinsing or Cleaning agents preferred that have been thawed after the wrapping process.

• a) Polyacrylsäuren und deren Salzen
• b) Polymethacrylsäuren und deren Salzen
• c) Polyvinylpyrrolidon,
• d) Vinylpyrrolidon/Vinylester-Copolymeren,
• e) Celluloseethern
• f) Polyvinylacetaten, Polyvinylalkoholen und ihren Copolymeren
• g) Pfropfcopolymeren aus Polyethylenglycolen und Vinylacetat
• h) Alkylacrylamid/Acrylsäure-Copolymeren und deren Salzen
• i) Alkylacrylamid/Methacrylsäure-Copolymeren und deren Salzen
• j) Alkylacrylamid/Methylmethacrylsäure-Copolymeren und deren Salzen
• k) Alkylacrylamid/Acrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymeren und deren Salzen
• l) Alkylacrylamid/Methacrylsäure/Alkylaminoalkyl(meth)acrylsäure -Copolymeren und deren Salzen
• m) Alkylacrylamid/Methylmethacrylsäure/Alkylaminoalkyl(meth)acrylsäure-Copolymeren und deren Salzen
• n) Alkylacrylamid/Alkymethacrylat/Alkylaminoethylmethacrylat/Alkylmethacrylat- Copolymeren und deren Salzen
• o) Copolymeren aus
  • 1. xiii-i) ungesättigten Carbonsäuren und deren Salzen
  • 2. xiii-ii) kationisch derivatisierten ungesättigten Carbonsäuren und deren Salzen
• p) Acrylamidoalkyltrialkylammoniumchlorid/Acrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• q) Acrylamidoalkyltrialkylammoniumchlorid/Methacrylsäure-Copolymere sowie deren Alkali- und Ammoniumsalze
• r) Methacroyl-ethylbetain/Methacrylat-Copolymere
• s) Vinylacetat/Crotonsäure-Copolymere
• t) Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere
• u) Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen
• v) gepropften Copolymere aus der Copolymerisation von
  • 1. xx-i) mindesten einem Monomeren vom nicht-ionischen Typ,
  • 2. xx-ii) mindestens einem Monomeren vom ionischen Typ,
• w) durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltenen Copolymere:
  • 1. xxi-i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesätigter Alkohole und ungesättigter Carbonsäuren,
  • 2. xxi-i) ungesättigte Carbonsäuren,
  • 3. xxi-iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe d6ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols.

Water-soluble polymers are particularly suitable as coating materials. Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature. In the context of the present invention, particular preference is given to using certain water-soluble polymers as coating materials. Detergent, dishwashing or cleaning agent portions according to the invention are preferred in which the wrapping material is selected from:

• a) Polyacrylic acids and their salts
• b) polymethacrylic acids and their salts
• c) polyvinylpyrrolidone,
• d) vinyl pyrrolidone / vinyl ester copolymers,
• e) cellulose ethers
• f) polyvinyl acetates, polyvinyl alcohols and their copolymers
• g) graft copolymers of polyethylene glycols and vinyl acetate
• h) alkyl acrylamide / acrylic acid copolymers and their salts
• i) alkyl acrylamide / methacrylic acid copolymers and their salts
• j) alkyl acrylamide / methyl methacrylic acid copolymers and their salts
• k) alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• l) alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• m) alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts
• n) alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and their salts
• o) copolymers
  • 1. xiii-i) unsaturated carboxylic acids and their salts
  • 2. xiii-ii) cationically derivatized unsaturated carboxylic acids and their salts
• p) Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
• q) Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
• r) Methacroyl ethyl betaine / methacrylate copolymers
• s) vinyl acetate / crotonic acid copolymers
• t) Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
• u) Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols
• v) grafted copolymers from the copolymerization of
  • 1. xx-i) at least one monomer of the non-ionic type,
  • 2. xx-ii) at least one monomer of the ionic type,
• w) copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
  • 1. xxi-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • 2. xxi-i) unsaturated carboxylic acids,
  • 3. xxi-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol.

The individual polymers mentioned above are described in more detail below:
Poly (meth) acrylic acids and their salts are described in detail below with the cobuilders.

Polyvinylpyrrolidones iii) are sold, for example, under the name Luviskol® (BASF). Polyvinylpyrrolidones are preferred polymers in the context of the present invention. Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (I)


which are produced by free-radical polymerization of 1-vinylpyrrolidone by solution or suspension polymerization using free-radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are presented as white, hygroscopic powders or as aqueous ones. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Vinylpyrrolidone / vinyl ester copolymers IV) are, for example, under the trademark Luviskol® (BASF) distributed. Luviskol® VA 64 and Luviskol® VA 73, each vinylpyrrolidone / vinyl acetate Copolymers are particularly preferred polymers.

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


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

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

Particularly suitable cellulose ethers v) are hydroxypropyl cellulose, hydroxyethyl cellulose and Methyl hydroxypropyl cellulose, such as those sold under the trademark Culminal® and Benecel® (AQUALON) are marketed.

Cellulose ethers can be described by the general formula (III)


in R represents H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are manufactured industrially by etherification of alkali cellulose (e.g. with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of cellulose have reacted with the etherification reagent or how many moles of etherification reagent have been attached to an anhydroglucose unit on average. Hydroxyethyl celluloses are soluble in water from a DS of approx. 0.6 or an MS of approx. 1. Commercial hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS). Hydroxyethyl and propyl celluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propyl celluloses are soluble in cold and hot water and in some (water-containing) organic solvents, but insoluble in most (water-free) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Other particularly preferred water-soluble polymers are polyvinyl acetals, polyvinyl alcohols and their copolymers. Among these, homopolymers of vinyl alcohol, copolymers of vinyl alcohol with copolymerizable monomers or hydrolysis products of vinyl ester homopolymers or vinyl ester copolymers with copolymerizable monomers are preferred. Homopolymers or copolymers of vinyl alcohol cannot be obtained by polymerizing vinyl alcohol (H ₂ C = CH-OH) since its concentration in tautomer equilibrium with acetaldehyde (H ₃ C-CHO) is too low. These polymers are therefore primarily prepared from polyvinyl esters, in particular polyvinyl acetates, via polymer-analogous reactions such as hydrolysis, but technically in particular by alkaline-catalyzed transesterification with alcohols (preferably methanol) in solution.

In the context of the present invention, polyvinyl alcohols are particularly preferred as water-soluble polymers. Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

which in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

contain.

Commercially available polyvinyl alcohols with white-yellowish powder or granules Degree of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol) are offered have degrees of hydrolysis of 98-99 or 87-89 mol%, so they still contain one Residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturers by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the Saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); from (chlorinated) They do not attack hydrocarbons, esters, fats and oils. Polyvinyl alcohols classified as toxicologically safe and are at least partially biodegradable. The Water solubility can be achieved by post-treatment with aldehydes (acetalization) Complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax reduce. The envelopes made of polyvinyl alcohol are largely impenetrable for gases such as Oxygen, nitrogen, helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.

Wrapping materials preferred in the context of the present invention are polyvinyl alcohol, whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used, those having a molecular weight in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , particularly preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 , are preferred.

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, particularly preferred between about 240 to about 1680 and especially between about 260 to about 1500th

The polyvinyl alcohols described above are widely available commercially, for example under the trademark Erkol® (from Erkol). Particularly within the scope of the present invention Suitable polyvinyl alcohols are, for example, Erkol® 3-83, Erkol® 4-88, Erkol® 5-88 and Erkol® 8-88.

Graft polymers of vinyl esters, esters of. Are also suitable as water-soluble polymers Acrylic acid or methacrylic acid alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols. Such grafted Polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture with other copolymerizable compounds on polyalkylene glycols by polymerization in the heat in a homogeneous phase by the fact that the polyalkylene glycols in the monomers the vinyl ester, ester of acrylic acid or methacrylic acid, is stirred in the presence of radical formers. Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, Vinyl benzoate and as esters of acrylic acid or methacrylic acid those with aliphatic Low molecular weight alcohols, in particular ethanol, propanol, isopropanol, 1- Butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1- Butanol, 1-hexanol, are available, proven.

Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polyethylene glycols are polymers of ethylene glycol which have the general formula IV

H- (O-CH ₂ -CH ₂ ) _n -OH (IV)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight after the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HÜLS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone -Poulenc), Lutrol® E300 (BASF) and the corresponding trade names with higher numbers.

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


are sufficient, where n can take values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycol, ie the representatives with n = 2, 3 and 4 in formula VI.

• - gepropfte und vernetzte Copolymere aus der Copolymerisation von
  • a) mindesten einem Monomeren vom nicht-ionischen Typ,
  • b) mindestens einem Monomeren vom ionischen Typ,
  • c) von Polyethylenglycol und
  • d) einem Vernetzter

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.

• - Grafted and crosslinked copolymers from the copolymerization of
  • a) at least one monomer of the non-ionic type,
  • b) at least one monomer of the ionic type,
  • c) of polyethylene glycol and
  • d) a networked person

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.

The monomers can be of very different types and among these are the following preferred: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allyl laurate, diethyl maleate, Allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene. The monomers of second group can equally be of very different types, among them particularly preferably crotonic acid, allyloxyacetic acid, vinyl acetic acid, maleic acid, acrylic acid and Methacrylic acid are contained in the graft polymers.

Ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallylsucrose with 2 to 5 allyl groups per molecule Saccharin.

• a) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
• b) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
• c) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und
• d) 0,1 bis 8 Gew.-% eines Vernetzters, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.

The grafted and crosslinked copolymers described above are preferably formed from:

• a) 5 to 85% by weight of at least one monomer of the non-ionic type,
• b) 3 to 80% by weight of at least one monomer of the ionic type,
• c) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
• d) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii).

Other suitable water-soluble polymers are copolymers of alkyl acrylamide with acrylic acid, Alkyl acrylamide with methacrylic acid, alkyl acrylamide with methyl methacrylic acid and Alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, Alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate Copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids, optionally other ionic or nonionic monomers.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers are amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers which contain quaternary ammonium groups and -COO in the molecule ^- - or -SO ₃ ^- contain groups, and summarized such polymers that contain -COOH or SO ₃ H groups and quaternary ammonium groups. An example of an amphopolymer which can be used according to the invention is the acrylic resin available under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group consisting of acrylic acid, Methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (e.g. acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (e.g. acrylamidopropyl-trimethyl-ammonium chloride) and optionally other ionic or nonionic monomers. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat®2001 N, are particularly preferred amphopolymers according to the invention. Other suitable amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).

Suitable zwitterionic polymers are, for example Acrylamidopropyltrimethyl-ammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts. Farther Suitable zwitterionic polymers are methacroyl ethyl betaine / methacrylate copolymers, which are listed below the name Amersette® (AMERCHOL) are commercially available.

• - Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn® (NATIONAL STARCH), Luviset® (BASF) und Gafset® (GAF) im Handel sind.
  Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (II) auch Monomereinheiten der allgemeinen Formel (VI) auf:
  
  [-CH(CH₃)-CH(COOH)-]_n (VI)
  
• - Vinylpyrrolidon/Vinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• - Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold® strong (BASF) vertrieben werden.
• - Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen

Anionic polymers suitable according to the invention include:

• - Vinyl acetate / crotonic acid copolymers, as are commercially available, for example, under the names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF).
  In addition to monomer units of the abovementioned formula (II), these polymers also have monomer units of the general formula (VI):
  
  [-CH (CH ₃ ) -CH (COOH) -] _n (VI)
  
• - Vinyl pyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex® (BASF). A preferred polymer is the vinylpyrrolidone / acrylate terpolymers available under the name Luviflex® VBM-35 (BASF).
• - Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, which are sold, for example, under the name Ultrahold® strong (BASF).
• - Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in a mixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols by Heat polymerization in a homogeneous phase obtained in that the polyalkylene glycols in the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in the presence of Radical generator stirs.

Suitable vinyl esters include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, Vinyl benzoate and as esters of acrylic acid or methacrylic acid those with aliphatic Low molecular weight alcohols, in particular ethanol, propanol, isopropanol, 1- Butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1- Butanol, 1-hexanol, are available, proven.

• a) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
• b) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
• c) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und
• d) 0,1 bis 8 Gew.-% eines Vernetzters, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.

The grafted and crosslinked copolymers described above are preferably formed from:

• a) 5 to 85% by weight of at least one monomer of the non-ionic type,
• b) 3 to 80% by weight of at least one monomer of the ionic type,
• c) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
• d) 0.1 to 8% by weight of a crosslinking agent, the percentage of the crosslinking agent being formed by the ratio of the total weights of i), ii) and iii).

• a) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesätigter Alkohole und ungesättigter Carbonsäuren,
• b) ungesättigte Carbonsäuren,
• c) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols

Copolymers obtained by copolymerization of at least one monomer from each of the following three groups are also suitable according to the invention as ingredient a):

• a) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
• b) unsaturated carboxylic acids,
• c) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol

Short-chain carboxylic acids or alcohols include those with 1 to 8 carbon atoms understand, the carbon chains of these compounds optionally by double-bonded Hetero groups such as -O-, -NH-, -S- can be interrupted.

Another particularly preferred class of polymers encased in those of the invention Portions that can be contained as wrapping material are polyurethanes. Are polyurethanes water-soluble in the sense of the invention if they are more than 2.5% by weight in water at room temperature are soluble.

• - einer Verbindung (A) mit mindestens 2 aktiven Wasserstoffatomen pro Molekül und
• - einem Di- oder Polyisocyanat (B).

The polyurethanes consist of at least two different types of monomers,

• - A compound (A) with at least 2 active hydrogen atoms per molecule and
• - a di- or polyisocyanate (B).

The compounds (A) can be, for example, diols, triols, diamines, triamines, Trade polyetherols and polyesterols. The connections with more than 2 active Hydrogen atoms usually only in small amounts in combination with a large one Excess of compounds with 2 active hydrogen atoms used.

Examples of compounds (A) are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, di-, Tri, tetra and poly ethylene and propylene glycols, copolymers of lower alkylene oxides such as Ethylene oxide, propylene oxide and butylene oxide, ethylene diamine, propylene diamine, 1,4-diaminobutane, Hexamethylenediamine and α, ω-diamines based on long-chain alkanes or polyalkylene oxides.

Polyurethanes in which the compounds (A) are diols, triols and polyetherols be preferred according to the invention. In particular with polyethylene glycols and polypropylene glycols Molar masses between 200 and 3000, in particular between 1600 and 2500, differ in individual Cases proven to be particularly suitable. Polyesterols are usually obtained by modifying the Compound (A) obtained with dicarboxylic acids such as phthalic acid, isophthalic acid and adipic acid.

The compounds (B) used are predominantly hexamethylene diisocyanate, 2,4- and 2,6-toluenediisocyanate, 4,4'-methylene di (phenyl isocyanate) and in particular isophorone diisocyanate. These compounds can be described by the general formula VII:

O = C = NR ¹ -N = C = O (VII),

in which R ^{1 represents} a connecting group of carbon atoms, for example a methylene-ethylene-propylene, butylene, pentylene, hexylene, etc. group. In the above-mentioned, most widely used hexamethylene diisocyanate (HMDI), R ⁴ = (CH ₂ ) ₆ , in 2,4- or 2,6-toluenediisocyanate (TDI) R ⁴ stands for C ₆ H ₃ -CH ₃ ) , in 4,4'-methylenedi (phenyl isocyanate) (MDI) for C ₆ H ₄ - CH ₂ -C ₆ H ₄ ) and in isophorone diisocyanate R ^{4 represents} the isophorone residue (3,5,5-trimethyl-2-cyclohexenone) ,

The polyurethanes used according to the invention can also contain building blocks such as, for example Contain diamines as chain extenders and hydroxycarboxylic acids. Dialkylol carboxylic acids such as for example, dimethylolpropionic acid are particularly suitable hydroxycarboxylic acids. Regarding there are no fundamental restrictions on the other building blocks as to whether they are nonionic, anionic or cationic building blocks.

For more information on the structure and manufacture of the polyurethanes expressly to the articles in the relevant reference works such as Römpps Chemie-Lexikon and Ullmann's Encyclopedia of Chemical Engineering.

• - ausschließlich aliphatische Gruppen im Molekül
• - keine freien Isocyanatgruppen im Molekül
• - Polyether- und Polyesterpolyurethane
• - anionische Gruppen im Molekül.

Polyurethanes, which can be characterized as follows, have proven particularly suitable according to the invention in many cases:

• - only aliphatic groups in the molecule
• - No free isocyanate groups in the molecule
• - Polyether and polyester polyurethanes
• - anionic groups in the molecule.

Particularly preferred polyurethanes contain at least some polyalkylene glycol units in the molecule. Envelopes are particularly preferred in which the water-soluble polymer (s) is / are selected from polyurethanes from diisocyanates (VII) and diols (VIII).

O = C = NR ¹ -N = C = O (VII),

HOR ² -OH (VIII),

the diols being selected at least in part from polyethylene glycols (IV) and / or polypropylene glycols (V)


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

The reaction mixtures can additionally contain further polyisocyanates. Also a salary of Reaction mixtures - and therefore the polyurethanes - on other diols, triplets, diamines, triamines, Polyetherols and polyesterols are possible. The connections with more than 2 active Hydrogen atoms usually only in small amounts in combination with a large one Excess of compounds with 2 active hydrogen atoms used.

If other diols etc. are added, there are certain quantitative ratios to those in the polyurethane existing polyethylene and / or polypropylene glycol units. Here are polyurethanes preferably in which at least 10% by weight, preferably at least 25% by weight, particularly preferably at least 50% by weight and in particular at least 75% by weight of those in the polyurethane reacted diols are selected from polyethylene glycols (IV) and / or polypropylene glycols (V).

Both in the case of compounds of the formula (IV) and in the case of compounds of the formula (V) those representatives preferred monomer units in which the number n is between 6 and 1500, preferably between 7 and 1200, particularly preferably between 8 and 1000, further preferably between 9 and 500 and in particular between 10 and 200. For certain Applications can be preferred polyethylene and polypropylene glycols of the formulas (IV) and / or (V) be in which n is a number between 15 and 150, preferably between 20 and 100, particularly preferably between 25 and 75 and in particular between 30 and 60.

Examples of optionally further contained in the reaction mixtures for the production of the polyurethanes Compounds are ethylene glycol, 1,2- and 1,3-propylene glycol, butylene glycols, ethylenediamine, Propylene diamine, 1,4-diaminobutane, hexamethylene diamine and α, ω-diamines based on long-chain Alkanes or polyalkylene oxides. Coatings in which the polyurethanes contain additional diamines, preferably hexamethylenediamine and / or hydroxycarboxylic acids, preferably Dimethylolpropionic acid are preferred.

Depending on which reactants are reacted with each other to form the polyurethanes, the result is polymers with different structural units. Portions according to the invention are preferred here in which the water-soluble polymer of the coating is a polyurethane which has structural units of the formula (IX)

- [OC (O) -NH-R ¹ -NH-C (O) -OR ² ] _k - (IX),

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

The diisocyanates described as preferred can be reacted with all the diols described as preferred to give polyurethanes, so that preferred coatings contain polyurethanes which have one or more of the structural units (IXa) to (IXh):

- [OC (O) -NH- (CH ₂ ) ₆ -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (IXa),

- [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (IXb),

- [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (IXc),

- [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) _n ] _k - (IXd),

- [OC (O) -NH- (CH ₂ ) ₆ -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - ( IXe)

- [OC (O) -NH- (2,4-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - (IXf),

- [OC (O) -NH- (2,6-C ₆ H ₃ -CH ₃ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) - CH ₂ ) _n ] _k - (IXg),

- [OC (O) -NH- (C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) -NH-C (O) -O-CH (CH ₃ ) -CH ₂ - (O-CH (CH ₃ ) -CH ₂ ) _n ] _k - (IXh),

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

As already mentioned above, the reaction mixtures in addition to diisocyanates (VII) and Diols (VIII) also other compounds from the group of polyisocyanates (in particular Triisocyanates and tetraisocyanates) and from the group of polyols and / or di- or polymains contain. In particular triols, tetrols, pentoles and hexols as well as di- and triamines can be used in the Reaction mixtures may be included. A content of compounds with more than two "active" H- Atoms (all classes of substances mentioned above with the exception of diamines) lead to a partial Crosslinking of the polyurethane reaction products and can have advantageous properties such as for example control of the dissolution behavior, abrasion stability or flexibility of the covering, Process advantages in manufacturing, etc. cause. The content is usually such Compounds with more than two "active" H atoms on the reaction mixture less than 20% by weight of the total reactants used for the diisocyanates, preferably less than 15% by weight and in particular less than 5% by weight.

In preferred embodiments of the present invention, the polyurethanes in the coatings have molar masses from 5000 to 150,000 gmol ^-1 , preferably from 10,000 to 100,000 gmol ^-1 and in particular from 20,000 to 50,000 gmol ^-1 .

The amounts in which the water-soluble polymer (s) in the coating are preferred contained, are 40 to 90 wt .-%, each based on the coating. preferred Envelopes are characterized in that they contain the water-soluble polymer (s) in Amounts from 45 to 87.5% by weight, preferably from 50 to 85% by weight, particularly preferably from 55 up to 82.5% by weight and in particular from 60 to 80% by weight.

Other preferred wrapping materials are meltable substances. Here are inventive Detergents, dishwashing detergents or cleaning agents are preferred, in which the casing has one or more fusible substances with a melting point in the range from 40 to 250 ° C., preferably from 42.5 to 220 ° C, particularly preferably from 45 to 200 ° C and in particular from 50 to 160 ° C.

A class of substances that is outstandingly suitable as a material for the coating are aliphatic and aromatic dicarboxylic acids, which can be melted individually, in a mixture with one another or also in a mixture with other substances and processed according to the invention for the coating. Particularly preferred dicarboxylic acids are summarized in the table below:

Instead of the dicarboxylic acids mentioned or in a mixture with them, the corresponding ones can also be used Anhydrides are used, which is particularly the case with glutaric acid, maleic acid and phthalic acid is advantageous.

In addition to the dicarboxylic acids, carboxylic acids and their salts are also suitable as materials for the production of the coating. From this class of substances, citric acid and trisodium citrate as well as salicylic acid and glycolic acid have proven to be particularly suitable. It is also particularly advantageous to use fatty acids, preferably those with more than 10 carbon atoms, and their salts as the material for the coating. Carboxylic acids which can be used in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. The use of fatty acids such as Dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid) and meltsiacetic acid (9) Hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid, 9tecadienoic acid ) and 9c, 12c, 15c-octadecatreic acid (linolenic acid) ends, it is preferable not to use the pure species but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _18''), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt _12% C, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _18''), tallow ( approx. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C _{16 '} , 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C _{18 '} , 3 wt% C _18'' , 1 wt% C _18''' ), hardened tallow fatty acid (approx. 2 wt% C ₁₄ , 28 wt% C ₁₆ , 2 wt% C ₁₇ , 63% by weight C ₁₈ , 1% by weight C _{18 '} ), technical oleic acid (approx. 1% by weight C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6 wt% C _{16 '} , 1 wt% C ₁₇ , 2 wt% C ₁₈ , 70 wt% C _18' , 10 wt% C _{18 '} , 0.5 wt% % C _{18 '''),} technical palmitic / stearic acid (about 1 wt .-% C _12, 2 wt .-% C ₁₄ 45 wt .-% C _16, 2 wt .-% C _17, 47 wt. % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (approx. 2% by weight C ₁₄ , 15% by weight C ₁₆ , 5% by weight C ₁₈ , 25% by weight C _{18 '} , 45% by weight C _18'' , 7% by weight C _18''' ).

The above-mentioned carboxylic acids are technically largely made from native fats and oils obtained by hydrolysis. During the past century Alkaline saponification led directly to the alkali salts (soaps) is now used on an industrial scale to split only water is used that splits the fats into glycerin and the free fatty acids. Industrially processes used are, for example, cleavage in the autoclave or continuous High pressure hydrolysis. The alkali metal salts of the abovementioned carboxylic acids or Carboxylic acid mixtures can - if necessary in a mixture with other materials - for the Use the manufacture of the cover.

Other suitable materials that can be processed for the coating via the state of the melt are hydrogen carbonates, in particular the alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate, and also the hydrogen sulfates, in particular alkali metal hydrogen sulfates, especially potassium hydrogen sulfate and / or sodium hydrogen sulfate. The eutectic mixture of potassium hydrogen sulfate and sodium hydrogen sulfate has also proven to be particularly suitable, which consists of 60% by weight of NaHSO ₄ and 40% by weight of KHSO ₄ .

Other suitable materials for wrapping, which process on the condition of the melt let are sugar. The term "sugar" denotes in the context of the present invention Single and multiple sugars, i.e. monosaccharides and oligosaccharides, in which 2 to 6 Monosaccharides are linked together like acetals. "Sugar" are within the scope of the present Invention thus monosaccharides, disaccharides, trisaccharides, tetra-, penta- and hexasaccharides.

Monosaccharides are linear polyhydroxy aldehydes (aldoses) or polyhydroxy ketones (ketoses). she usually have a chain length of five (pentoses) or six (hexoses) carbon Atoms. Monosaccharides with more (heptoses, octoses etc.) or fewer (tetroses) carbon atoms kinda rare. Monosaccharides sometimes have a large number of asymmetric carbon atoms. For a hexose with four asymmetric carbon atoms results in a number of 24 stereoisomers. The orientation of the OH group at the highest numbered asymmetric carbon atom in the Fischer Projection divides the monosaccharides into D- and L-configured rows. Of course occurring D-configuration is much more common. Form monosaccharides, if possible, intramolecular hemiacetals so that ring-shaped structures (Pyranoses) and furan type (furanoses). Smaller rings are unstable, larger rings only in aqueous solutions resistant. The cyclization creates another asymmetric carbon atom (the so-called anomeric carbon atom), which doubles the number of possible stereoisomers. This is prefixed by α- u. expressed in β. The formation of the hemiacetals is a dynamic process which depends on various factors such as temperature, solvent, pH, etc. Mostly are mixtures of both anomeric forms, sometimes also as mixtures of furanose and Pyranose forms.

Monosaccharides which can be used as sugar in the context of the present invention are, for example the tetroses D (-) - erythrose and D (-) - threose and D (-) - erythrulose, the pentoses D (-) - ribose, D (-) - Ribulose, D (-) - arabinose, D (+) - xylose, D (-) - xylulose and D (-) - lyxose and the hexoses D (+) - allose, D (+) - Altrose, D (+) - Glucose, D (+) - Mannose, D (-) - Gulose, D (-) - Idose, D (+) - Galactose, D (+) - Talose, D (+) - psicose, D (-) - fructose, D (+) - sorbose and D (-) - tagatose. The most important and the farthest common monosaccharides are: D-glucose, D-galactose, D-mannose, D-fructose, L-arabinose, D- Xylose, D-ribose and the like. 2-deoxy-D-ribose.

Disaccharides are made from two simple monosaccharide linked by glycosidic bonds Molecules (D-glucose, D-fructose, etc.) built. The glycosidic bond lies between the acetalic carbon atoms (1 for aldoses or 2 for ketoses) of both monosaccharides, so so that the ring shape fixed in both; the sugars show no mutarotation, do not react with ketone Reagents and no longer have a reducing effect (Fehling negative: Trehalose or sucrose type). In contrast, the glycosidic bond connects the acetal carbon atom to one Monosaccharides with any of the second, so this can still take the open chain form, and the sugar has a reducing effect (Fehling positive: maltose type).

The main disaccharides are sucrose (cane sugar, sucrose), trehalose, lactose (Milk sugar), lactulose, maltose (malt sugar), cellobiose (breakdown product of cellulose), Gentobiose, Melibiosis, Turanose and others.

Trisaccharides are carbohydrates that consist of 3 glycosidically linked monosaccharides are built up and for which you sometimes come across the incorrect term trios. Trisaccharides are relatively rare in nature, examples are gentianose, kestose, maltotriose, Melecitose, raffinose, and as an example of amino sugar-containing trisaccharides streptomycin and Validamycin.

Tetrasaccharides are oligosaccharides with 4 monosaccharide units. Examples of this Compound classes are stachyose, lychnose (galactose-glucose-fructose-galactose) and secalose (from 4-fructose units).

In the context of the present invention, saccharides from the group are preferred as sugars Glucose, fructose, sucrose, cellubiosis, maltose, lactose, lactulose, ribose and their Mixtures used.

Another particularly preferred material for the coating is urea, the diamide of carbonic acid, which is sometimes also referred to as carbamide and can be described by the formula H ₂ N-CO-NH ₂ . Urea forms colorless, odorless crystals with a density of 1.335, which melt at 133 ° C. Urea is soluble in water, methanol, ethanol and glycerin with a neutral reaction. Especially when mixed with other substances, urea is an excellent material for the coating. So z. B. non-ionic surfactants, fragrances, dyes, etc. are melted in large quantities together with the urea and processed into an open casing without impairing the mechanical and haptic properties of the casing. Mixtures of urea and nonionic surfactants which contain up to 50% by weight of nonionic surfactant, based on the mixture, are particularly preferred.

Other suitable materials, some of the above-mentioned meltable substances in High amounts can be added are silicates, phosphates and / or starches.

When processing the melts for coating, it can be advantageous to add additives to the Introduce melting. In addition to the colors used for aesthetic reasons, and fragrances, for example disintegration aids, reinforcing fibers or liquid Binder proved to be particularly suitable. Disintegration tools are discussed below described in detail; as reinforcing fibers such. B. natural or synthetic Polymer fibers into consideration. Microcrystalline cellulose is also suitable as an additive.

In summary, washing, rinsing or cleaning agents according to the invention are preferred in which the coating one or more substances from the groups of dicarboxylic acids, Dicarboxylic anhydrides, hydrogen carbonates, hydrogen sulfates and / or urea in amounts of at least 10% by weight, preferably at least 20% by weight and in particular at least 35% by weight, each based on the mass of the casing.

It can be advantageous to place disintegration aids, so-called "disintegrants", in the casing incorporated to accelerate their decay. Under disintegrants or accelerators are according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical Technologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances which are necessary for the rapid disintegration of Tablets in water or gastric juice and for the release of pharmaceuticals in absorbable form to care.

These substances, which are also referred to as "explosives" due to their effect, enlarge Water ingress their volume, whereby on the one hand the own volume increases (swelling), on the other hand A pressure can also be generated via the release of gases, which breaks the tablet down into smaller ones Particles disintegrate. Well-known disintegration aids are, for example Carbonate / citric acid systems, whereby other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as Polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and Starch and its derivatives, alginates or casein derivatives.

Preferred coatings contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the Wrapping weight.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred coatings contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not in finely divided form used, but converted into a coarser form before the admixing to the casings, for example granulated or compacted. The particle sizes of such disintegrants are mostly above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90% by weight between 400 and 1200 µm. The above and Coarse cellulose-based disintegration aids described in more detail in the cited documents are to be used in the context of the present invention as disintegration aids and commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier available.

As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial Hydrolysis of celluloses obtained under conditions that only the amorphous areas (approx. Attack 30% of the total cellulose mass) of the celluloses and completely dissolve the crystalline ones Leave areas (approx. 70%) undamaged. A subsequent disaggregation by the Hydrolysis resulting microfine celluloses provides the microcrystalline celluloses Have primary particle sizes of about 5 microns and for example to granules with a medium Particle size of 200 microns can be compacted.

The portions according to the invention can be used as detergents, as cleaning agents or as detergents be assembled. In addition to textile detergents, cleaning agents for the machine or manual dishwashing, universal household cleaners, toilet cleaners, glass cleaners etc. manufacture. Depending on the application, the selection of ingredients in the processing washing, rinsing or flowing at room temperature Detergent compositions may be different. Important ingredients of this Compositions are described below.

The washing, rinsing or cleaning agent compositions that flow at room temperature preferably contain surfactant (s), being anionic, nonionic, cationic and / or amphoteric Surfactants are used. From an application point of view, textile detergents are preferred Mixtures of anionic and nonionic surfactants, the proportion of anionic surfactants should be greater than the proportion of nonionic surfactants. The total surfactant content of the laundry, The detergent or cleaning agent composition is preferably below 30% by weight on the entire mean.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO , C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks, but statistically. Such products can be obtained from the simultaneous action of ethylene and propylene oxide on fatty alcohols.

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

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

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula X,


in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula XI


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

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

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

In machine dishwashing detergents are preferably used as low-foaming nonionic Surfactants used. Machine tools according to the invention particularly preferably contain Dishwashing detergent is a nonionic surfactant that has a melting point above room temperature having. Accordingly, preferred agents are characterized in that they are nonionic (s) Surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, contain.

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

Preferred nonionic surfactants to be used as solid at room temperature come from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures thereof 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.

In a preferred embodiment of the present invention, the nonionic surfactant is included a melting point above room temperature an ethoxylated nonionic surfactant, which results from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 moles, in particular at least 20 moles, of ethylene oxide per mole Alcohol or alkylphenol has emerged.

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

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _18-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably make such PO units up to 25 wt .-%, particularly preferably up to 20 wt .-% and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or Alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight such non-ionic surfactants. Preferred rinse aids are characterized in that they are ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass make up the nonionic surfactant included.

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

Examples of nonionic surfactants that can be used with particular preference are available under the name Poly Tergent® SLF-18 from Olin Chemicals.

A further preferred rinse aid according to the invention contains nonionic surfactants of the formula

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

in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y stands for a value of at least 15.

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

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

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

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

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

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

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

If the latter statements are summarized, rinse aids according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

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

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

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

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

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

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


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

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the □ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerol can be obtained. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.

As alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Saturated ones are suitable and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, (hydrogenated) erucic acid and behenic acid and in particular from natural Fatty acids, e.g. B. coconut, palm kernel, olive oil or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

The content of anionic surfactants in preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the entire mean.

In the context of the present invention, preferred agents additionally contain one or more Substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, Hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, Graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, Ironing aids, phobing and impregnating agents, swelling and anti-slip agents as well as UV absorbers.

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

The use of the generally known phosphates as builder substances is possible according to the invention, unless such use should be avoided for ecological reasons. Under the A large number of the commercially available phosphates have the alkali metal phosphates in particular Preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.

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

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

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ³ , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the salt of water free of crystal water dissolve at room temperature, about 20 g at 60 ° and about 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

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

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystals of zeolite X and zeolite A (approx. 80% by weight zeolite X ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

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

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

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

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

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

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

In addition, other ingredients may be present, washing, rinsing or Cleaning agents are preferred which additionally contain one or more substances from the group of Acidifying agents, chelating agents or the deposit-inhibiting polymers contain.

Both inorganic acids and organic acids are suitable as acidifiers, if they are compatible with the other ingredients. For consumer protection reasons and the handling safety are in particular the solid mono-, oligo- and polycarboxylic acids used. From this group, preference is again given to citric acid, tartaric acid, succinic acid, Malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Also the Anhydrides of these acids can be used as acidifying agents, in particular Maleic anhydride and succinic anhydride are commercially available. organic Sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as Acidifying agent is also preferably used in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), Glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

Another possible group of ingredients are the chelating agents. Chelating agents are substances that form cyclic compounds with metal ions single ligand occupies more than one coordination site on a central atom, d. H. min. is "bidentate". In this case, stretched connections are normally used Complex formation closed by an ion to form rings. The number of ligands bound depends on the coordination number of the central ion.

Common chelate complex images which are preferred in the context of the present invention are for example polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and Nitrilotriacetic acid (NTA). Also complex-forming polymers, i.e. polymers that are either in the Main chain itself or laterally to this functional groups that act as ligands can and with suitable metal atoms usually with the formation of chelate complexes react, can be used according to the invention. The polymer-bound ligands of the resulting Metal complexes can originate from just one macromolecule or different ones Polymer chains belong. The latter leads to the networking of the material, provided that the complex-forming Polymers were not previously cross-linked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, Hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, Aminophosphoric acid, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether residues with, for. T. very specific Activities against ions of different metals. Many base polymers too commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, Polyvinyl alcohols, polyvinyl pyridines and polyethylene imines. Even natural polymers like cellulose, Starch or chitin are complex-forming polymers. Furthermore, this can be done through polymer-analogous conversions can be provided with further ligand functionalities.

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

in Mengen oberhalb von 0,1 Gew.-%, vorzugsweise oberhalb von 0,5 Gew.-%, besonders bevorzugt oberhalb von 1 Gew.-% und insbesondere oberhalb von 2,5 Gew.-%, jeweils bezogen auf das Gewicht des Geschirrspülmittels, enthalten. In the context of the present invention, detergents, dishwashing detergents or cleaning agents which contain one or more chelate complexing agents from the groups of

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

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

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

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

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

Polycarboxylic acids a) are carboxylic acids in the context of this patent application Monocarboxylic acids - understood, in which the sum of carboxyl and those in the molecule contained hydroxyl groups is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, especially EDTA, are preferred. In the invention These complex bilgeers are the required alkaline pH values of the treatment solutions at least partially as anions. It is immaterial whether they are in the form of acids or in the form of Salts are introduced. When used as salts are alkali, ammonium or Alkyl ammonium salts, especially sodium salts, are preferred.

Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from Groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, where Polymers with molecular weights below 15,000 daltons are preferred.

Deposit-inhibiting polymers can also have cobuilder properties. As organic Cobuilders can be used in particular in the dishwasher detergents according to the invention Polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, Dextrins, other organic cobuilders (see below) and phosphonates can be used. This Substance classes are described below.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these. Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.

The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and are therefore also used for Setting a lower and milder pH value for detergents or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.

Polymeric polycarboxylates are also suitable as builders or scale inhibitors, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{W of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated.

This information differs significantly from the molecular weight information for which polystyrene sulfonic acids be used as standard. The molar masses measured against polystyrene sulfonic acids are in generally significantly higher than the molar masses specified in this document.

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

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

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

Also particularly preferred are biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of the monomers Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. More preferred Copolymers are those which, as monomers, preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids and their salts or to name their precursors. Polyaspartic acids or their salts and derivatives, which in addition to cobuilder properties also have a bleach-stabilizing effect exhibit.

Other suitable builder substances are polyacetals, which are reacted with dialdehydes Polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or Obtain glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The Hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes become. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500000 g / mol. Here is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, are preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100, is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups can be used with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher ones Molar masses in the range from 2000 to 30000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferred in Form of its sodium or magnesium salts used. Are further preferred in this Also related to glycerol disuccinates and glycerol trisuccinates. Suitable amounts are used in zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight.

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

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as Co-builders. It is preferably used as the sodium salt, the disodium salt being neutral and the Tetrasodium salt reacts alkaline (pH 9). Preferred aminoalkane phosphonates are Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta and octa Sodium salt of DTPMP, used. As a builder, the class of phosphonates preferably HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred to use aminoalkanephosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition to the substances from the substance classes mentioned, the agents according to the invention can contain further common ingredients of washing, rinsing or cleaning agents, in particular Bleaches, bleach activators, enzymes, silver preservatives, colors and fragrances are important. These substances are described below.

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

To improve the bleaching effect when washing at temperatures of 60 ° C and below achieve, bleach activators can be incorporated into the detergent tablets become. Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid result can be used. Suitable substances are the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2, 5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called Bleaching catalysts can be incorporated into the moldings. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru, or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Enzymes include, in particular, those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry in laundry to remove stains such as protein, fat or starchy stains and graying. Cellulases and other glycosyl hydrolases can also by the Removal of pilling and microfibrils to preserve color and increase the softness of the textile contribute. Oxireductases can also be used to bleach or inhibit color transfer be used. Bacterial strains or fungi such as Bacillus are particularly suitable subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens enzymatic agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic Enzymes or protease and cellulase or from cellulase and lipase or lipolytic Enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, Lipase or lipolytic enzymes and cellulase, but especially protease and / or Mixtures containing lipase or mixtures with lipolytically active enzymes are particularly useful Interest. Known cutinases are examples of such lipolytically active enzymes. Also Peroxidases or oxidases have proven to be suitable in some cases. To the appropriate ones Amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As Cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which too Cellobiases are called, or mixtures of these are used. Because there are different Cellulase types can be distinguished by their CMCase and avicelase activities by targeted Mixtures of cellulases to set the desired activities.

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

The cleaning agents according to the invention can protect the dishes or the machine Corrosion inhibitors contain, especially silver protection in the field of mechanical Dishwashing have a special meaning. The known substances of State of the art. In general, silver protection agents can be selected from the group of Triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the Transition metal salts or complexes are used. Are particularly preferred to use Benzotriazole and / or alkylaminotriazole. You will also often find it in detergent formulations Agents containing active chlorine, which can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners are especially oxygen and nitrogen-containing organic redox-active Compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also salt-like and complex-like 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 that are selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the Cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the Chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used Prevention of corrosion on the wash ware.

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

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

In order to bring the pH of the agents according to the invention into the desired range, the Use of pH adjusting agents. All known acids or Alkalis, provided that their use is not for technical or ecological reasons or banned for reasons of consumer protection. Usually the amount exceeds this Adjusting agent 5% by weight of the total formulation not.

In order to improve the aesthetic impression of the agent according to the invention, you can use suitable dyes are colored. Preferred dyes, their selection to the expert no difficulty, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity compared to textile fibers so as not to stain them.

Foam inhibitors that can be used in the agents according to the invention come for example soaps, paraffins or silicone oils, which may be on carrier materials may be upset. Suitable anti-redeposition agents, also known as soil repellents are, for example, nonionic cellulose ethers such as methyl cellulose and Methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30 wt .-% and Hydroxypropyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of this. Particularly preferred of these are the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention to remove graying and yellowing of the treated textiles. These substances draw on the fiber and cause a lightening and feigned bleaching effect by Convert invisible ultraviolet radiation into visible longer-wave light, which is from the Sunlight absorbed ultraviolet light as a faint bluish fluorescence and is emitted with the yellow tone of the grayed or yellowed laundry results in pure white. Suitable connections originate, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (Flavonic acids), 4,4'-distyryl-biphenylene, methylumbelliferone, coumarins, dihydroquinolinones, 1,3- Diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well of pyrene derivatives substituted by heterocycles. The optical brighteners are usually in Amounts between 0.05 and 0.3 wt .-%, based on the finished agent, used.

Graying inhibitors have the task of removing the dirt detached from the fiber in the liquor to keep suspended and thus prevent the dirt from re-opening. For this are Suitable water-soluble colloids mostly organic, for example glue, gelatin, salts of Ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Water-soluble polyamides containing acidic groups are also for this Suitable purpose. Soluble starch preparations and others other than those mentioned above can also be used Use starch products, e.g. B. degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful. However, cellulose ethers such as carboxymethyl cellulose (sodium salt) are preferred, Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures in amounts of 0.1 up to 5 wt .-%, based on the agent used

If the agents according to the invention are packaged as agents for automatic dishwashing, so other ingredients can be used. Machine-washed dishes are used today Often higher demands are placed on hand-washed dishes. So one of Food residues of fully cleaned dishes are then rated as not perfect if they are after machine dishwashing still whitish, on water hardness or other mineral salts shows stains that come from dried water drops due to the lack of wetting agents. To obtain crystal-clear and spotless dishes, rinse aid is therefore used successfully today. The addition of rinse aid at the end of the wash program ensures that the water is as possible runs completely from the wash ware, so that the different surfaces at the end of the Washing programs are residue-free and spotlessly shiny. Machine cleaning of dishes in Domestic dishwashers typically include a pre-wash, a main wash and a rinse cycle that is interrupted by intermediate rinse cycles. Most machines the pre-wash cycle for heavily soiled dishes can be switched on, but is only used in exceptional cases chosen by the consumer, so that in most machines a main wash, a Intermediate rinse cycle with pure water and a rinse cycle should be carried out. The temperature The main wash cycle varies between 40 and depending on the machine type and program level selection 65 ° C. In the rinse aid, rinse aid is added from a dosing tank in the machine usually contain non-ionic surfactants as the main ingredient. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is in preventing limescale and deposits on the dishes.

The agents according to the invention can be formulated as "normal" cleaners, which together with commercially available supplements (rinse aid, regeneration salt). With However, the additional dosage can be particularly advantageous with the products according to the invention rinse aid should be dispensed with. These so-called "2in1" products lead to one Simplify handling and take away the burden of additional dosage from the consumer two different products (detergent and rinse aid).

Even when using "2in1" products are in operation for operating a household dishwasher Intervals two dosing processes required, because after a certain number of The regeneration salt in the water softening system of the machine got to. These water softening systems consist of ion exchange polymers, which the Soften the machine's incoming hard water and use a washing machine after the wash program Rinsing with salt water can be regenerated.

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

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

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

contain.

These copolymers have the effect that the dishes treated with such agents are used in subsequent ones Cleaning processes become significantly cleaner than tableware using conventional means were rinsed.

As an additional positive effect, the drying time with the cleaning agent is reduced treated dishes on d. H. the consumer can after the cleaning program remove the dishes from the machine earlier and reuse them.

The invention features improved "cleanability" of the treated substrates compared to later cleaning processes and by significantly reducing the drying time comparable agents without the use of sulfonic acid-containing polymers.

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

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

R ¹ (R ² ) C = C (R ³ ) COOH (XV),

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

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

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

R ⁵ (R ⁶ ) C = C (R ¹ ) -X-SO ₃ H (XVI),

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

Preferred among these monomers are those of the formulas VIIIa, VIIIb and / or VIIIc,

H ₂ C = CH-X-SO ₃ H (XVIa),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (XVIb),

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (XVIc),

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 represents an optionally present spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula XVIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula XVIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula XVIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH- CH (CH ₃ ) CH ₂ - in formula XVIb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C (O) NH-CH ₂ CH (OH) CH ₂ - in formula XVIb), allylsulfonic acid (X = CH ₂ in formula XVIa), methallylsulfonic acid (X = CH ₂ in formula XVIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XVIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula XVIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid (X = CH ₂ in formula XVIb), styrene sulfonic acid (X = C ₆ H ₄ in formula XVIa), vinyl sulfonic acid (X not present in formula XVIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in Formula XVIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula XVIb), sulfomethacrylamide (X = -C (O) NH- in formula XVIb), sulfomethyl methacrylamide (X = - C (O) NH-CH ₂ - in formula XVIb) and water-soluble salts of the acids mentioned.

Other ionic or nonionic monomers in particular are ethylenically unsaturated Connections into consideration. The content of those used according to the invention is preferably Polymers on monomers of group iii) less than 20% by weight, based on the polymer. Especially Polymers to be used preferably consist only of monomers of groups i) and ii).

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

besonders bevorzugt. In summary, copolymers are made of

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

particularly preferred.

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

Particularly preferred copolymers consist of

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

The copolymers which are contained in the agents according to the invention can be the monomers from the groups i) and ii) and optionally iii) in varying amounts, with all representatives from the group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred polymers have certain structural units, which are described below.

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

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

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

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

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

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

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

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

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

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

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

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

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

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _r - 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 and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XXI

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

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

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

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

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

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

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

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

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

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

The sulfonic acid groups in the polymers can be wholly or partly in neutralized form are present, d. H. that the acidic hydrogen atom of the sulfonic acid group in some or all Sulphonic acid groups against metal ions, preferably alkali metal ions and in particular against Sodium ions, can be exchanged. Corresponding means, which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized, are according to the invention prefers.

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

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

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

The content of one or more copolymers in the agents according to the invention may vary Vary application and desired product performance, preferred preferred according to the invention automatic dishwashing detergents are characterized in that they contain the copolymer (s) in Quantities from 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, particularly preferably from Contain 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.

As already mentioned above, the agents according to the invention are particularly preferred both polyacrylates and the above-described copolymers of unsaturated Carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic ones or non-ionic monomers. The polyacrylates were discussed in detail above described. Combinations of those described above are particularly preferred Copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in Range between 1000 and 4000 daltons. Such polyacrylates are commercially available under the Trade names Sokalan® PA15 or Sokalan® PA25 (BASF) available.

The agents according to the invention can also be packaged as fabric softeners or washing additives become. Depending on the intended use, additional ingredients can be used.

Fabric softener compositions for rinse bath finishing are wide in the prior art described. These compositions usually contain a cationic active substance quaternary ammonium compound which is dispersed in water. Depending on the content of the finished Plasticizer composition of active substance is called diluted, ready-to-use Products (active substance contents below 7% by weight) or so-called concentrates (Active substance content over 7% by weight). Because of the lower volume and at the same time Reduced packaging and transport costs have advantages for the fabric softener concentrates from an ecological perspective and have become more and more established in the market. Due to the Incorporation of cationic compounds that are only slightly soluble in water Usual fabric softener compositions in the form of dispersions have a milky cloudy Appearance and are not translucent. For reasons of product aesthetics, it can also be desired to provide the consumer with translucent, clear fabric softener that stand out visually from the known products.

Portioned fabric softeners according to the invention contain as fabric softening active substance preferably cationic surfactants, which have already been described in detail above (formulas XII, XIII and XIV). Particularly preferably contain "fabric softener portions" according to the invention so-called ester quats. While there are a variety of possible connections from this Substance class there are used according to the invention with particular preference esterquats that by reacting trialkanolamines with a mixture of fatty acids and dicarboxylic acids, optionally subsequent alkoxylation of the reaction product and quaternization in itself can be produced in a known manner, as described in DE 195 39 846.

The esterquats produced in this way are outstandingly suitable for production Portions according to the invention which can be used as fabric softeners. Since depending on the choice of Trialkanolamines, fatty acids and dicarboxylic acids as well as the quaternizing agent A large number of suitable products are produced and used in the agents according to the invention can, is a description of the ester quats to be preferably used according to the invention their route of manufacture more precisely than the specification of a general formula.

The components mentioned together with each other to form the preferred esterquats react, can be used in varying proportions to each other. As part of Portioned fabric softeners containing a reaction product are preferred in the present invention of trialkanolamines with a mixture of fatty acids and dicarboxylic acids in a molar ratio 1:10 to 10: 1, preferably 1: 5 to 5: 1, which optionally alkoxylates and then in itself was quaternized in a known manner, in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-% is included. The use of triethanolamine is particularly preferred, so that further preferred portioned fabric softener of the present invention is a reaction product of triethanolamine with a mixture of fatty acids and dicarboxylic acids in a molar ratio 1:10 to 10: 1, preferably 1: 5 to 5: 1, which optionally alkoxylates and then in itself was quaternized in a known manner, in amounts of 2 to 60, preferably 3 to 35 and in particular Contain 5 to 30 wt .-%.

As fatty acids, all of them can be used in the reaction mixture to produce the esterquats Vegetable or animal oils and fats acids can be used. It can in Recation mixture as a fatty acid is also a non-solid at room temperature, i.e. H. pasty up liquid, fatty acid can be used.

The fatty acids can be saturated or one or more times, regardless of their physical state be unsaturated. Of course, not only "pure" fatty acids can be used, but also the technical fatty acid mixtures obtained from the cleavage of fats and oils, whereby from an economic point of view, these mixtures are clearly preferred.

So can in the reaction mixtures for the preparation of the ester quats for the clear aqueous fabric softener according to the invention, for example individual species or mixtures use the following acids: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, Palmitic acid, stearic acid, octadecan-12-ol acid, arachic acid, behenic acid, lignoceric acid, Cerotic acid, melissic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, Elaidic acid, ricinoleic acid, linolaidic acid, α- and β-eläosterainic acid, gadoleic acid, erucic acid, Brassidic. Of course, the fatty acids with an odd number of carbon atoms are also usable, for example undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, Nonadecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid.

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

R ¹ -CO-OH (XXII)

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

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

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

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

Among the multitude of esterquats that can be produced and used in accordance with the invention are Again, those in which the alkanolamine treithanolamine and the Dicarboxylic acid is adipic acid. Thus, means are special in the context of the present invention preferred, which is a reaction product of triethanolamine with a mixture of fatty acids and Adipic acid in a molar ratio of 1: 5 to 5: 1, preferably 1: 3 to 3: 1, which then in itself was quaternized in a known manner, in amounts of 2 to 60, preferably 3 to 35 and in particular 5 to 30 wt .-% contained in the agents

Depending on whether they are used as textile detergents, Washing aids or fabric softeners are formulated - also equipped with additional benefits become. For example, here are color transfer inhibiting compositions, agents with "anti Gray formula ", agent with ironing relief, agent with special fragrance release, agent with improved dirt removal or prevention of re-soiling, antibacterial agents, UV protection agents, color-refreshing agents, etc. can be formulated. Some examples are given below explains:

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

To control microorganisms, the agents according to the invention can be antimicrobial Contain active ingredients. A distinction is made depending on the antimicrobial spectrum and Mechanism of action between bacteriostatics and bactericides, fungistatics and fungicides etc.

Important substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, Halogenphenols and Phenolmercuriacetat, with the agents according to the invention also entirely these connections can be dispensed with.

To unwanted, caused by oxygen and other oxidative processes The agents can prevent changes to the agents and / or the treated textiles Contain antioxidants. This class of compounds includes, for example, substituted phenols, Hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, Dithiocarbamates, phosphites and phosphonates.

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

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

Finally, the agents according to the invention can also contain UV absorbers which act on the treated textiles and improve the lightfastness of the fibers. Connections that these desired properties are, for example, those due to non-radiation Deactivation of active compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Substituted benzotriazoles are also substituted in the 3-position by phenyl Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid are suitable.

As already mentioned above, the portioned compositions according to the invention can also be used Mix conventional washing, rinsing or cleaning agents, both frozen Portions, as well as coated and thawed portions can be mixed - in the former case would be the cold chain is needed again. Of course, you can also use several according to the invention Prepare detergent, dishwashing or cleaning agent portions of different compositions and mix them together. Again, there is a mixture of wrapped and uncoated Servings possible without any problems. Suffering from the multitude of possibilities are exemplary here Mixing of frozen, coated and thawed liquid enzyme preparations with commercially available Heavy duty detergents or the blending of a conventional frozen liquid detergent called particulate sodium percarbonate or sodium tetraborate. Another subject of The present invention is therefore a solid detergent, dishwashing or cleaning agent composition, containing at least one portioned solid washing, rinsing or Detergent and / or at least one portioned portioned thawed test according to the invention Detergent, dishwashing detergent or cleaning agent.

Another object of the present invention is the use of frozen, portioned, solid preparations as washing, rinsing or cleaning agents.

The use of frozen, portioned, solid and coated preparations as washing, rinsing or detergent, as disclosed above, is an object of the present invention.

Last but not least, the wrapped portions can also be used beyond the cold chain, so that the use of frozen, portioned, firm, coated and subsequently thawed Preparations as washing, rinsing or cleaning agents, a further subject of the present Invention is.

Claims (22)

1. A process for the preparation of portioned solid washing, rinsing or cleaning agents, characterized in that a washing, rinsing or cleaning agent composition which is flowable at room temperature is frozen in a shaping manner. 2. The method according to claim 1, characterized in that the flowable at room temperature Detergent, dishwashing or cleaning agent composition poured into molds, frozen and is subsequently removed from the mold. 3. The method according to claim 1, characterized in that the flowable at room temperature Detergent, dishwashing or cleaning agent composition by introducing it into a cooling stream pelletized, twisted, pastilled or flaked. 4. The method according to claim 3, characterized in that the flowable at room temperature Detergent, dishwashing or cleaning agent composition in a cooling stream of a liquid Coolant is introduced, at least frozen in the cooling stream to form pellets and is then removed from the cooling stream, the cooling stream preferably as horizontal cooling flow is generated by directed forced flow in a coolant bath and a liquid pump is particularly preferably used to generate the cooling stream. 5. The method according to any one of claims 3 or 4, characterized in that the pellets in Frozen cooling stream, discharged from the cooling stream by means of a conveyor and on the conveyor are frozen out under the action of a gaseous coolant, wherein preferably the cold exhaust air of the liquid coolant is used as the gaseous coolant. 6. The method according to any one of claims 1 to 5, characterized in that the frozen washing Dishwashing or cleaning agent composition in a subsequent process step is enveloped. 7. The method according to claim 6, characterized in that the covering by application molten wrapping materials, water-soluble wrapping materials are preferred. 8. The method according to any one of claims 6 or 7, characterized in that the thickness of the Coating is 0.1 to 500 microns, preferably 5 to 200 microns and in particular 10 to 150 microns. 9. The method according to any one of claims 6 to 8, characterized in that the enveloped portioned detergents, dishwashing detergents or cleaning agents can be thawed before packing. 10. A process for the preparation of portioned, liquid, coated compositions, thereby characterized in that a composition flowable at room temperature gives shape frozen, encased in a subsequent process step and after encasing is thawed. 11. Portioned solid washing, rinsing or cleaning agent, characterized in that it is a Temperature below 0 ° C, preferably below -5 ° C, particularly preferably below of -10 ° C, more preferably below -15 ° C and in particular below -18 ° C, having. 12. washing, rinsing or cleaning agent according to claim 11, characterized in that it Temperature increase to room temperature becomes fluid. 13. washing, rinsing or cleaning agent according to one of claims 11 or 12, characterized characterized in that it has particle sizes of 0.5-10 mm, preferably from 1 to 7.5 mm and in particular from 1.5 to 5 mm. 14. washing, rinsing or cleaning agent according to one of claims 11 or 12, characterized characterized in that it is 0.1 to 20 times, preferably 0.25 to 10 times, particularly preferably 0.5 to 5 times and in particular one to three times the amount for one Washing, rinsing or cleaning cycle required dosage units. 15. washing, rinsing or cleaning agent according to one of claims 11 to 14, characterized characterized that it is encased. 16. washing, rinsing or cleaning agent according to claim 15, characterized in that it after the wrapping process has been thawed. 17. washing, rinsing or cleaning agent according to one of claims 15 or 16, characterized characterized in that the coating one or more meltable substances with a Melting point in the range from 40 to 250 ° C, preferably from 42.5 to 220 ° C, particularly preferably from 45 to 200 ° C and in particular from 50 to 160 ° C. 18. washing, rinsing or cleaning agent according to one of claims 15 to 17, characterized characterized in that the coating one or more substances from the groups of Dicarboxylic acids, dicarboxylic anhydrides, hydrogen carbonates, hydrogen sulfates and / or Urea in amounts of at least 10% by weight, preferably at least 20% by weight and contains in particular at least 35% by weight, based in each case on the mass of the casing. 19. Solid detergent, dishwashing or cleaning composition containing at least one portioned solid washing, rinsing or cleaning agent according to claim 11 and / or at least one wrapped portioned detergent, dishwashing or cleaning agent according to Claim 15. 20. Use of frozen, portioned, solid preparations as washing, rinsing or Cleaning supplies. 21. Use of frozen, portioned, solid and coated preparations as washing, rinsing or Cleaning supplies. 22. Use of frozen, portioned, firm, coated and subsequently thawed Preparations as washing, rinsing or cleaning agents.