DE10058647A1 - Portions of laundry, dish-washing or other detergent in dimensionally-stable hollow molding(s) with at least one compartment, used especially in commercial machine machines and for cleaning - Google Patents

Abstract

Portions (A) of laundry, dish-washing or other detergent in dimensionally-stable hollow molding(s) with at least one compartment comprise: (a) at least one detergent formulation (I); (b) that is (partly) surrounded by an uncompressed material (II) that gives the molding dimensional stability and can disintegrate; and (c) optionally partition(s) dividing the molding(s) into compartments. Independent claims are also included for: (a) portions (B) of laundry and other detergents in the form of hollow moldings sub-divided into >= 2 (partly) filled compartments surrounded by (I); (b) portions (C) of laundry and other detergents (partly) comprising solidified material; (c) methods of producing portions of detergents in hollow moldings with compartment(s); and (d) a method of producing hollow moldings.

Description

The present application is an additional application to the German patent application 100 33 827.5 (filing date: July 14, 2000). The parent application relates to a detergent, cleaning agent or detergent portion contained in one or more dimensionally stable hollow body (s) with at least one compartment

• a) at least one wash-active, cleaning-active or rinse-active preparation;
• b) at least one completely or partially surrounding at least one preparation according to (a) Enclosure of a disintegrable under washing, cleaning or rinsing conditions, the non-pressed material imparting dimensional stability to the hollow body (s); and
• c) optionally one or more device (s) for compartmentalizing the dimensionally stable Hollow body (s).

The parent application also relates to a method for producing such a detergent, Serving of detergent or detergent as well as washing processes, cleaning processes and Rinsing process using such a detergent, cleaning agent or detergent Portion.

According to a preferred embodiment of the parent application, the dimensionally stable Hollow bodies produced by so-called casting techniques. This additional application is available the field of this particular embodiment.

The detergent, cleaning agent or detergent portions disclosed in the parent application consist of an outer hollow form that contains one or more fillings. The Hollow form can be divided into several compartments by partitions, creating multiple fillings can be present separately from one another within the same hollow body. At the fillings apart from the compatibility with the material of the hollow mold, no requirements are made, so that both solid and liquid phases (systems) can be portioned.  

The production of the outer hollow molds can be done economically by so-called Casting techniques take place, and this technology is the greatest possible flexibility with regard to processing to form the hollow mold and with regard to the material systems used. all Pouring techniques in common is the forming of a flowable mixture, which under suitable Conditions are frozen. The present application discloses a method for Production of hollow bodies in this way and that which can be produced from the hollow bodies Servings of detergent, detergent or detergent.

The invention relates to a method for producing portioned detergents or cleaning agents, comprising the steps:

• a) production of an open hollow mold by solidification;
• b) filling the hollow mold with detergent or cleaning agent;
• c) optionally closing the mold.

The production of the open hollow mold includes the provision of a deformable, preferably flowable mixture or such a substance and solidification into one dimensionally stable hollow shape. "Solidification" denotes in the context of the present invention any curing mechanism that consists of a formable, preferably flowable Mixture or such a substance or such a mass a solid at room temperature Body delivers, without pressing or compacting forces are necessary. "Freeze" in the sense of The present invention is therefore, for example, the curing of melts from Substances solid at room temperature by cooling. "Solidification processes" in the sense of The present application is also the curing of deformable masses by delayed Water retention, through evaporation of solvents, through chemical reaction, crystallization etc. as well as the reactive hardening of flowable powder mixtures to form stable hollow bodies. How already carried out in the parent application include tableting, pelleting, briquetting processes etc., so pressing process, not in this category.

In summary, methods according to the invention are preferred in which the open hollow shape is formed by water retention delayed by cooling below the melting point, by evaporation of Solvents, by crystallization, by chemical reaction (s), in particular polymerization, by changing the rheological properties e.g. B. by changing shear, by sintering or produced by means of radiation curing, in particular by UV, alpha, beta or gamma rays becomes.

The solidification mechanisms mentioned are described in detail below.

It is not necessary for the implementation of the method according to the invention that the open Hollow mold made and z. B. is temporarily stored until filling. Rather, steps i) and ii) the method according to the invention can also be carried out simultaneously by one  Hollow mold is filled "in situ", ie directly during its manufacture. This is particularly the case with Manufacture of hollow molds from self-solidifying masses (e.g. by cooling under the Melting point or by delayed water binding) can be easily realized by using a Two-component nozzle, which is constructed like a Daniellian tap, the filling inside and the outside Material for the hollow mold can be metered into a mold. This in detail below The "one-shot" process described allows the economical production of large quantities of moldings.

Accordingly, methods according to the invention are preferred in which steps i) and ii) are carried out simultaneously be performed.

Of course, the method according to the invention is also carried out step by step Step "possible, so that, for example, hollow bodies are produced and subsequently filled Technology includes the possibility of the formulation of the washing or filled in step ii) Change detergent without having to adapt the procedure. Especially with washing or cleaning agents that cannot be dosed or cannot be dosed well via two-substance nozzles are recommended this approach. Also methods in which steps i) and ii) are carried out in succession are preferred embodiments of the present invention.

Regardless of whether the manufacture of the "shell" (the open hollow form) before filling or at the same time as this, the shell manufacture includes informing a deformable Mixture that solidifies during or after the informing to the open hollow form ("stiffens"). The formable mixture, which can also consist of a single substance, can are in the form of a powder, a liquid, a gel, a melt, etc., each depending according to the composition of one or more of the solidification mechanisms mentioned above come to fruition.

From a process economics point of view, melts are particularly preferred because they are simple Cool below the melting point and solidify and are generally easy to process. Therefore are The method according to the invention is particularly preferred in which the production of the open hollow mold in Step i) takes place by solidification of a melt, the melt consisting of a material, whose melting point in the range from 40 to 1000 ° C, preferably from 42.5 to 500 ° C, particularly preferably from 45 to 200 ° C. and in particular from 50 to 160 ° C.

Substances that are particularly suitable for carrying out this variant of the method according to the invention are, for example, polyethylene glycols

H- (O-CH ₂ -CH ₂ ) _n -OH

in which the degree of polymerization n can assume values between approximately 30 and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. It is technically common to specify the average relative molecular weight after the  Specification "PEG", so that "PEG 200" is a polyethylene glycol with a relative molecular weight of approx. 190 to characterized about 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and a number directly after the hyphen follows, which corresponds to the number n in the above formula. Are commercially available Polyethylene glycols, for example, under the trade names Carbowax® PEG (Union Carbide), Emkapol® (ICI Americas), Lipoxol® (HÜLS America), Polyglycol® E (Dow Chemical), Alkapol® PEG (Rhone-Poulenc), Lutrol® E (BASF).

The molar masses of preferred polyethylene glycols are in the range between 1500 and 35000 daltons, preferably between 2000 and 30000 Da, particularly preferably between 3000 and 25000 Da and especially between 4000 and 20000 Da.

Polypropylene glycols (abbreviation PPG) can also be used

where the degree of polymerization n also values between about 30 and several thousand can accept. With regard to the molecular weights of PPG to be used with preference, this applies analogously to PEG said.

The polyethylene or polypropylene glycols can be mixed with others with particular advantage Substances are used as shell material. Particularly suitable additives to the Polyalkylene glycols are polymers or polymer mixtures, the polymer or at least 50% by weight of the polymer mixture is selected from graft copolymers which are obtainable by Grafting (a) polyalkylene oxides with (b) vinyl acetate. These polymers are discussed in more detail below described.

Suitable in the context of the present invention as an additive to polyalkylene glycols Graft copolymers are described in European patent application EP 219 048 A (BASF). They are obtainable by grafting a polyalkylene oxide with vinyl acetate, the acetate groups of Vinyl acetates can be partially saponified. In particular, polymers come as polyalkylene oxides Ethylene oxide, propylene oxide and butylene oxide units into consideration, with polyethylene oxide being preferred is.

The graft copolymers can be prepared, for example, by dissolving the polyalkylene oxides in Vinyl acetate and continuous or batch polymerization after adding a Polymerization initiator, or by semi-continuous polymerization, in which a part of the Polymerization mixture of polyalkylene oxide, vinyl acetate and polymerization initiator Polymerization temperature is heated, after which the rest of the mixture to be polymerized is added becomes. The graft copolymers can also be obtained by polyalkylene oxide  submitted, heated to the polymerization temperature and vinyl acetate and polymerization initiator either at once, batchwise or preferably continuously.

Processes preferred in the context of the present invention use in step i) melts from polyalkylene glycols which contain at least one polymer which can be obtained by grafting (a) polyalkylene oxides having a molecular weight of 1500 to 70,000 gmol ^-1 with (b) vinyl acetate in a weight ratio of (a): (b) from 100: 1 to 1: 5, the acetate groups optionally being saponified up to 15%. In preferred embodiments of the present invention, the molecular weight of the polyalkylene oxides contained in the graft copolymers is 2000 to 50,000 gmol ^-1 , preferably 2500 to 40,000 gmol ^-1 , particularly preferably 3000 to 20,000 gmol ^-1 and in particular 4000 to 10,000 gmol ^-1 .

Depending on the desired properties of the open hollow shape, the proportion of individual monomers of the graft copolymers added to the melt vary. There are polymers preferred in which the vinyl acetate content is 1 to 60% by weight, preferably 2 to 50% by weight, particularly preferably 3 to 40 wt .-% and in particular 5 to 25 wt .-%, each based on the Graft copolymer.

A graft copolymer which is particularly preferred in the context of the present invention is based on a polyethylene oxide with an average molecular weight of 6000 gmol ^-1 (corresponding to 136 ethylene oxide units) which contains about 3 parts by weight of vinyl acetate per part by weight of polyethylene oxide. This polymer, which has an average molecular weight of approx. 24000 gmol ^-1 , is sold commercially by BASF under the name Sokalan® HP22.

Another class of substances which is outstandingly suitable as a material for the open hollow form are aliphatic and aromatic dicarboxylic acids which can be melted individually, in a mixture with one another or in a mixture with other substances and processed according to the invention. 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 open hollow form. 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 material for the open hollow form. 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), docosanoic 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) It is preferred 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 .-% C _{18 '1} wt .-% C _{18 "),} palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% C _12, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _{18 "),} tallow fatty acid (about 3 % By weight C ₁₄ , 26% by weight C ₁₆ , 2% by weight C _{16 '} , 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight C _18' , 3 % By weight C _{18 "} , 1% by weight C _{18 '''} , hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight C ₁₇ , 63 wt .-% C _18: 1 wt .-% C _18), African technical oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt .-% C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 "} , 0.5% by weight C _{18 '''} ), technical palmitin / stearic acid (approx. 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 oleic acid (approx. 2% by weight C ₁₄ , 15 Wt .-% C _16, 5 wt .-% C _18, 25 wt .-% C _{18 ',} 45 wt .-% C _{18 ",} 7 wt .-% 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 a large 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 open mold.

Other suitable materials that can be processed into open hollow molds via the state of the melt are hydrogen carbonates, in particular the alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate, and 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 the open hollow form, which can be found in step i) of the invention Processes about the state of the melt are processed into sugars. The term "sugar in the context of the present invention denotes single and multiple sugars, ie Monosaccharides and oligosaccharides in which 2 to 6 monosaccharides are acetal-like with each other are connected. "In the context of the present invention, sugars are therefore 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 monosaccharides, the D configuration is far 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 value 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 (-) - Guiose, 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 composed of 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 Monosaccharide with any of the second, 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 (cellulose breakdown product), Gentobiose, Melibiosis, Turanose and others.

Trisaccharides are carbohydrates that consist of 3 glycosidically linked monosaccharides are constructed and for which one occasionally encounters the incorrect term trios. Trisaccharides are relatively rare in nature, examples are gentianose, kestose, maltotriose, Melecitose, raffinose, and streptomycin as an example of trisaccharides containing amino sugar 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 open hollow form 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 hollow mold. So z. B. polyethylene and propylene glycols, fragrances, dyes, etc. are melted in large quantities together with the urea and processed into the open mold without impairing the mechanical and tactile properties of the mold.

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 to form an open hollow mold, it can be advantageous to add additives to the mold 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 aids are in the parent registration 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, methods according to the invention are preferred in which the melt in step i) one or more substances from the groups of carboxylic acids, carboxylic anhydrides, Dicarboxylic acids, dicarboxylic acid anhydrides, hydrogen carbonates, hydrogen sulfates, polyethylene glycols, Polypropylene glycols, sodium acetate trihydrate and / or urea in amounts of at least 40% by weight, preferably at least 60% by weight and in particular at least 80% by weight, in each case based on the melt, contains.

The formable mixtures can solidify by different mechanisms, the time-delayed water binding, the evaporation of solvents, the crystallization, the chemical reaction (s), in particular polymerization, the change in the rheological Properties e.g. B. by changing the shear of the mass (s), and the radiation curing by UV, Alpha beta or gamma rays as the most important hardening mechanisms in addition to those already mentioned Cooling below the melting point should be mentioned.

The solidification takes place in processes which are likewise preferred within the scope of the present invention due to delayed water binding.

The time-delayed water binding can be realized in different ways become. There are, for example, raw materials or raw material mixtures that can be hydrated, anhydrous raw materials or raw materials in low hydration levels that result in stable higher hydrates can pass over, as well as contain water. The formation of the hydrates, which does not occur spontaneously, leads then to bind free water, which in turn causes the mixtures to harden Formation of the hollow form leads. Thereafter, shaping processing with low pressures is not more possible, and there are handling-stable hollow bodies.

The time-delayed water binding can also take place, for example, in that salts containing hydrate water, which dissolve in their own crystal water when the temperature rises, in the masses incorporated. If the temperature drops later, the crystal water is bound again, what to a loss of formability with simple means and a solidification of the Leads masses.

The swelling of natural or synthetic polymers is also delayed Water binding mechanism can be used in the process according to the invention. Here  Mixtures of unswollen polymer and suitable swelling agent, e.g. B. water, diols, Glycerin etc., are incorporated into the masses, with swelling and curing after the Shaping takes place.

The most important mechanism of hardening by delayed water binding is the use a combination of water and water-free or low-water raw materials that slowly hydrate. For this purpose, there are in particular substances that are used in the washing or cleaning process Contribute to cleaning performance. Preferred in the process according to the invention Ingredients of the hollow forms are, for example, phosphates, carbonates, silicates and zeolites. It is particularly preferred if the hydrate forms formed have low melting points, because in this way a combination of the curing mechanisms through internal drying and Cooling is achieved. Preferred methods are characterized in that the Starting materials for the hollow mold 10 to 95 wt .-%, preferably 15 to 90 wt .-%, particularly preferably contain 20 to 85% by weight and in particular 25 to 80% by weight of anhydrous substances, which by hydration into a hydrate form with a melting point below 120 ° C, preferably pass below 100 ° C and in particular below 80 ° C.

The deformable properties can be added by adding plasticizers such as Polyethylene glycols, polypropylene glycols, waxes, paraffins, nonionic surfactants etc. to be influenced. More detailed information on the substance classes mentioned can be found above or in the parent registration.

Raw materials to be used preferably in the manufacture of the open hollow molds originate from the Group of phosphates, with alkali metal phosphates being particularly preferred. These substances will used in the production in anhydrous or poor form and the desired plastic or deformable properties of the masses with water and optional plasticizing aids set. After the shaping processing, the molded part is then cured Hollow forms through hydration of the phosphates.

Alkali metal phosphates have been described in detail in the parent application.

In preferred processes, the mixtures used to produce the hollow molds contain Phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 20 to 80% by weight, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on it Weight.

If phosphates are used as the only hydratable substances, the amount of added should Water whose water binding capacity does not exceed the free content of the hollow body To keep water low. Overall, have adhered to the above limits  Processes found to be preferred in which the weight ratio of phosphate (s) to Water in the mixtures for producing the hollow molds less than 1: 0.3, preferably less than 1: 0.25 and in particular less than 1: 0.2.

Other ingredients that may be included in place of or in addition to phosphates are Carbonates and / or bicarbonates, the alkali metal salts and among them especially the Potassium and / or sodium salts are preferred. This also applies here with regard to the water content Said above. In particular, methods have been found to be preferred for which the weight ratio of carbonate (s) and / or hydrogen carbonate (s) to water in the Mixtures for producing the hollow molds less than 1: 0.2, preferably less than 1: 0.15 and is in particular less than 1: 0.1.

Other ingredients instead of or in addition to the phosphates mentioned and / or Carbonates / bicarbonates can be contained are silicates, the alkali metal silicates and especially the amorphous and / or crystalline potassium and / or sodium disilicate are preferred. The statements made above also apply here with regard to the water content of the masses.

Above was the weight ratio of water to certain ingredients in According to the invention, preference is given to mixtures to be processed into hollow bodies. After Processing this water is preferably bound in the form of water of hydration, so that the in Step i) produced hollow molds preferably have a significantly lower free water content exhibit. Preferred cavity molds are essentially anhydrous, i.e. H. in a condition when which the content of liquid, i.e. H. not in the form of water of hydration and / or constitutional water water present below 2% by weight, preferably below 1% by weight and in particular even below 0.5 wt .-%, based in each case on the moldings. Accordingly, water can essential only in chemically and / or physically bound form or as part of the as Solid raw materials or compounds, but not as a liquid, solution or dispersion are present in the end products of step i). Advantageously, the hollow body at the end of the Manufacturing process a total water content of not more than 15 wt .-%, wherein this water is not in liquid, free form, but chemically and / or physically bound is present, and it is particularly preferred that the content of not zeolite and / or silicates bound water in the solid premix not more than 10% by weight and in particular not more than 7% by weight.

Hollow molds which are particularly preferred in the context of the present invention have not only one extremely low proportion of free water, but are preferably still able to to bind more free water. In preferred processes, the water content of the hollow molds is 50 to 100% of the calculated water binding capacity.

The water binding capacity is the ability of a substance (here: the hollow form) to absorb water in a chemically stable form and ultimately indicates how much water can be bound by a substance or a shaped body in the form of stable hydrates. The dimensionless value of the water binding capacity (WBV) is calculated from:

where n is the number of water molecules in the corresponding hydrate of the substance and M is the molar mass of the non-hydrated substance. This results, for example, in the water-binding capacity of anhydrous sodium carbonate (formation of sodium carbonate monohydrate)

The value WBV can be used for all hydrate-forming substances in the according to the invention Hollow molds to be used for processing mixtures are calculated. About the percentages of these substances then result in the total water binding capacity of the Recipe. In preferred hollow forms, the water content is then between 50 and 100% of this calculated value.

In addition to the water content of the hollow molds and the ratio of water to certain raw materials can also provide information about the absolute water content of those to be processed according to the invention Mixtures are made. In particularly preferred methods, the have / have to produce of the mixtures used for the hollow molds has a water content of 2.5 to 30% by weight, preferably from 5 to 25% by weight and in particular from 7.5 to 20% by weight, in each case based on mass, on.

In summary, method variants according to the invention are preferred in which the production the open mold in step i) is carried out by time-delayed water binding, the solidifying mass based on its weight 10 to 95 wt .-%, preferably 15 to 90 wt .-%, particularly preferably 20 to 85% by weight and in particular 25 to 80% by weight of anhydrous substances contains, which harden through hydration.

Another mechanism by which the solidification to the hollow shape in step i) of the invention Process can be done is the evaporation of solvents. Solutions or Dispersions of the desired ingredients in one or more suitable, volatile Solvent (s) are produced which, after the shaping processing step, this (s) Dispense solvent and harden. Lower solvents, for example, are available as solvents Alkanols, aldehydes, ethers, esters, etc., their selection depending on the further composition of the processing mixtures is made. Particularly suitable solvents for such Processes are 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 and the acetic acid esters of the aforementioned alcohols, especially ethyl acetate.

The evaporation of the solvents mentioned can follow the shaping Warming, or accelerated by air movement. Combinations of the above Measures are suitable for this, for example blowing the hollow body with warm or Hot air.

Processes according to the invention are preferred here in which the production of the open hollow mold in Step i) is carried out by evaporation of solvents, the solidifying mass based on it Weight 1 to 50% by weight, preferably 2 to 40% by weight and in particular 5 to 30% by weight contains evaporable solvents.

Another mechanism of solidification to the hollow form in step i) of the invention The process may be based on crystallization.

Crystallization as the mechanism underlying solidification can be used by for example melting crystalline substances as the basis for one or more shaping agents processable mixtures. After processing, such systems go to a higher one Ordered state, which in turn leads to hardening of the entire hollow body formed. The Crystallization can also be carried out by crystallization from supersaturated solution. In the context of the present invention, supersaturation is the name for one metastable state in which there is more of a substance in a closed system, than is necessary for saturation. A supersaturated one obtained, for example, by hypothermia Accordingly, solution contains more solute than it should contain in thermal equilibrium. The excess of dissolved substance can by vaccination with germs or dust particles or by Shake the system to be crystallized. As part of the present Invention, the term "oversaturated" always refers to a temperature of 20 ° C.

The term “solubility” is understood by the present invention to mean the maximum amount of a substance which the solvent can absorb at a certain temperature, d. H. the share of the solved Substance in a solution saturated at the temperature in question. Contains one more solution solute than they are in thermodynamic equilibrium at a given temperature should contain (e.g. with solvent evaporation), it is called supersaturated. By vaccinating with Germination can cause the excess as the bottom of the now only saturated solution fails. However, a solution saturated with one substance is capable of other substances dissolve (e.g. you can still dissolve sugar in a saturated saline solution).

The state of supersaturation can be, as described above, by cooling a solution achieve as long as the solute is more soluble in the solvent at higher temperatures.  

Other ways of achieving supersaturated solutions are, for example, unification two solutions, the ingredients of which react to another substance that does not fail immediately (prevented or delayed precipitation reactions). The latter mechanism is the basis the formation of mixtures to be processed according to the invention is particularly suitable.

In principle, the state of supersaturation can be achieved with any type of solution, even if the Application of the principle described in the present application as already mentioned in the Manufacture of detergents and cleaning agents is used. As a result, some systems which in principle tend to form supersaturated solutions, are less usable according to the invention because the underlying material systems are not ecological, toxicological or for economic reasons can be used. In addition to non-ionic surfactants or common non-aqueous ones Solvents are therefore methods according to the invention with the latter Curing mechanism particularly preferred, in which as a basis at least one processing mixture, a supersaturated aqueous solution is used.

As mentioned above, the state of supersaturation relates to the present invention on the saturated solution at 20 ° C. By using solutions that have a temperature above 20 ° C, the state of supersaturation can easily be reached become. Processes according to the invention, in which the mixture solidifying by crystallization processing a temperature between 35 and 120 ° C, preferably between 40 and 110 ° C, between 45 and 90 ° C and in particular between 50 and 80 ° C, are particularly preferred preferred in the context of the present invention.

Since the hollow bodies produced are usually neither stored at elevated temperatures nor later applied at these elevated temperatures, the mixture will cool Precipitation of the proportion of solute from the supersaturated solution that exceeds the saturation limit was contained in the solution at 20 ° C. The supersaturated solution can thus cool down divide a saturated solution and a soil body. But it is also possible that through Recrystallization and hydration phenomena the supersaturated solution when cooling to one Solid solidifies. This is the case, for example, when there are certain hydrated salts dissolve in their crystal water when heated. When cooling, supersaturated ones often form here Solutions that become a solid by mechanical action or the addition of germs salt containing water of crystallization as the state thermodynamically stable at room temperature - solidify. This phenomenon is known for example from sodium thiosulfate pentahydrate and Sodium acetate trihydrate, in particular the latter hydrate-containing salt in the form of supersaturated solution can be used advantageously in the process according to the invention. Even special ones Detergent and detergent ingredients, such as phosphonates, show this phenomenon and in the form of the solutions are ideal as granulation aids. For this, dis appropriate phosphonic acids (see below) neutralized with concentrated alkali water, whereby the solution is heated by the heat of neutralization. When cooling, these solutions form Solids of the corresponding alkali phosphonates. By incorporating further washing and  Detergent ingredients in the still warm solutions can be inventively Produce processable masses of different compositions. Particularly preferred Methods according to the invention are characterized in that as the basis of the solidifying Mixing supersaturated solution solidified to a solid at room temperature. Prefers is here that the previously supersaturated solution after solidification to a solid by heating to the temperature at which the supersaturated solution was formed, not back into a supersaturated one Solution can be transferred. This is the case, for example, with the phosphonates mentioned.

The supersaturated solution serving as the basis for the solidifying mixture can - as above mentioned - received in several ways and then after optional addition of further ingredients are processed according to the invention. A simple way is, for example, that the as Basis of the solidifying mixture serving supersaturated solution by dissolving the dissolved Fabric is made in heated solvent. Be heated this way Solvent higher amounts of the dissolved substance than would dissolve at 20 ° C, so lies a supersaturated solution in the sense of the present invention, which is either hot (see above) or cooled and can be brought into shape in the metastable state.

It is also possible to dehydrate salts containing hydrate by "dry" heating and in dissolve your own crystal water (see above). This is also a method within which to produce presently applicable supersaturated solutions.

Another way is to make a non-supersaturated solution with a gas or another To move liquid or solution so that the solute in the solution to a worse soluble substance reacts or dissolves poorly in the mixture of solvents. Uniting two solutions, each containing two substances, which together form a less soluble Reacting substance is also a method of producing supersaturated solutions as long as the poor soluble substance does not fail immediately. Also within the scope of the present invention preferred methods are characterized in that the as the basis of the solidifying Mixing supersaturated solution made by combining two or more solutions becomes. Examples of such ways to make supersaturated solutions are discussed below.

Preferred methods according to the invention are characterized in that the supersaturated aqueous Solution by combining an aqueous solution of one or more acidic ingredients of washing and cleaning agents, preferably from the group of surfactant acids, builder acids and Complexing acids, and an aqueous alkali solution, preferably an aqueous Alkali hydroxide solution, in particular an aqueous sodium hydroxide solution, is obtained.

Take among the representatives of the connection classes mentioned above in particular the phosphonates in the context of the present invention have an outstanding position on. In preferred processes according to the invention, therefore, the supersaturated aqueous solution is passed through Combining an aqueous phosphonic acid solution with concentrations above 45% by weight,  preferably above 50% by weight and in particular above 55% by weight, in each case based on the Phosphonic acid solution and an aqueous sodium hydroxide solution with concentrations above 35 % By weight, preferably above 40% by weight and in particular above 45% by weight, in each case based on the sodium hydroxide solution.

According to the invention, the solidifying mixture (s) can also be cured by chemical means Rekation (s), in particular polymerization, take place. In principle, all are chemical Suitable reactions based on one or more liquid to pasty substances Reaction with (another) substance (s) leads to solids. Especially chemical reactions, that do not suddenly lead to the state change mentioned are suitable. From diversity Chemical reactions that lead to the solidification phenomenon are reactions in particular suitable in which larger molecules are built up from smaller molecules. Which includes again prefers reactions in which many small molecules become (one) larger molecule (s) react. These are so-called polyreactions (polymerization, polyaddition, polycondensation) and polymer-analogous reactions. The corresponding polymers, polyadducts (polymer addition products) or polycondensates (polycondensation products) then give the finished hollow body its Strength.

In view of the intended use of the products produced according to the invention, it is preferred as Curing mechanism the formation of such solid substances from liquid or pasty To use raw materials that are in the washing and cleaning agents anyway as ingredients, for example cobuilders, should-repellents or should-release polymers are to be used. Such Cobuilders can, for example, polymerize from the groups of polycarboxylates / polycarboxylic acids Polycarboxylates, aspartic acid, polyacetals, dextrins, etc. These classes of substances are in of the parent application.

Another mechanism according to which the hardening of the solidifying mixture (s) within the framework of the can be done by changing the rheological method Properties curing.

It takes advantage of the property that certain substances under the influence of Shear forces sometimes change their rheological properties drastically. Examples of such Systems which are known to the person skilled in the art are, for example, layered silicates which are sheared in suitable matrices have a strong thickening effect and can lead to cut-resistant masses.

Of course, two or more can also be used in a solidifying mixture Hardening mechanisms are linked or used simultaneously. Here offer themselves for example, crystallization with simultaneous evaporation of the solvent, cooling simultaneous crystallization, water binding ("internal drying") with simultaneous external Drying etc.  

Another preferred mechanism, according to the malleable, preferably flowable mixture can solidify is sintering. The sintering represents the provision of one in the form of the later hollow body preformed particle aggregate, which under the influence of external Conditions (temperature, radiation, reactive gases, liquids, etc.) in one compact Hollow body part is transferred. Examples of sintering processes are those from the prior art known production of moldings by microwaves or radiation curing.

Another preferred sintering process for the production of hollow bodies is reactive sintering. The starting components are brought into shape and then solidified by a Component A and a component B are reacted with one another, the Components A and B mixed with the starting components, applied to them or after Inform bring be added.

When this method is carried out, components A and B react to solidify the individual ingredients together. The reaction product formed from components A and B. connects the individual starting components in such a way that a firm, relatively break-resistant Hollow body is obtained.

With this method, hollow bodies with good decay are obtained. Because the bond of individual ingredients by reactive sintering and not by the "stickiness" of the Granules of the premix is conditional, it is not necessary to match the recipe to the binding properties of the individual ingredients. These can be any depending on their effectiveness be adjusted.

In order to cause components A and B to react with one another, it has proven to be advantageous if the starting components are mixed with component A or coated with them before they are brought into shape. Examples of compounds of component A are the alkali metal hydroxides, in particular NaOH and KOH, alkaline earth metal hydroxides, in particular Ca (OH) ₂ , alkali silicates, organic or inorganic acids, such as citric acid, or acidic salts, such as hydrogen sulfate, anhydrous, hydratable salts or salts containing hydrate water, such as soda , Acetates, sulfates, alkali metalates, where the abovementioned compounds can, if possible, also be used in the form of their aqueous solutions.

Component B is selected such that it reacts with component A without the application of higher pressures or a substantial increase in temperature, with the formation of a solid, with solidification of the other starting components present. Examples of compounds of component B are CO ₂ , NH ₃ , water vapor or spray, salts containing hydrate water, which may react with the anhydrous salts present as component A by hydrate migration, hydrated salts which form hydrates and the salts of the component containing hydrate water A react with hydrate migration, SO ₂ , SO ₃ , HCl, HBr, silicon halides such as SiCl ₄ or Kiselsäureester S (OR) _x R ' _4-x .

Components A and B above are interchangeable, provided two Components are used that react with one another during sintering.

In a preferred embodiment of this production route, the starting components are mixed or coated with compounds of component A and then mixed with the compounds of component B. It has proven particularly suitable if the compounds of component B are gaseous. The molded components (hereinafter referred to as preforms) can then either be gassed in a simple form or introduced into a gas atmosphere. A particularly preferred combination of components A and B are concentrated solutions of the alkali metal hydroxides, in particular NaOH and KOH, and alkaline earth metal hydroxides, such as Ca (OH) ₂ , or alkali metal silicates as component A and CO ₂ as component B.

To carry out process step i) according to the invention, the starting components are first brought into shape, ie they are usually filled into a die which has the outer shape of the hollow body to be produced. The starting components are preferably in powdery to granular form. First, they are mixed or coated with component A. After filling into the die or mold, it has proven to be preferred to press the starting components lightly, e.g. B. by hand or with a stamp at a pressure which is below the above values, in particular below 100 N / cm ² . It is also possible to compress the premix by vibration (knock compression).

Subsequently, if component A is not already mixed with the Starting components are present, coated with them and mixed with component B. After expiration the reaction gives a breakable hollow body without the action of pressure or temperature.

If one of the components A or B is a gas, a preform may e.g. B. be offset with this so that the gas flows through it. This procedure enables a uniform hardening of the molded body within a short time.

In a further process variant, a preform is placed in an atmosphere of the reactive gas brought in. This variant is easy to carry out. It is possible to manufacture hollow bodies that have a hardness gradient, d. H. Hollow bodies that only have a hardened surface up to towards hollow bodies that are fully hardened.

A preform or the premix can also be reacted with the reactive gas under excess pressure become. This process variant has the advantage that the surface quickly forms a hard shell hardens, the hardening process already being stopped here or how  Fully hardened can also be described above with increasing hardening stages Moldings are produced.

The above process variants can also be combined by first allows reactive gas to flow through the preform to displace air. Then you bet the preform of a gas atmosphere at normal pressure. Through the reaction between the gas and the second component is automatically sucked gas into the molding.

In one possible embodiment of the present invention, the starting mixture does not but coated a preform already formed with component A and then reacted with component B. It hardens itself on the surface of the Preform layer, while in the core the loose or slightly compressed structure preserved. Hollow bodies of this type are distinguished by particularly good disintegration behavior.

In summary, process variants are also preferred in which the production of the open Hollow mold in step i) is carried out by sintering, the flowable mixture Exposure to temperature or chemical reaction is solidified.

Regardless of the mechanism of solidification in the manufacture of the hollow mold The method according to the invention is preferred, in which the hollow mold produced in step i) has wall thicknesses from 100 to 6000 µm, preferably from 120 to 4000 µm, particularly preferably from 150 to 3000 µm and in particular from 200 to 2500 microns, with wall thicknesses below 2000 microns in turn are preferred.

The hollow mold in step i) can be produced using different techniques, some of which depend on the type of solidification mechanism. In the simplest case, it becomes flowable The mixture is poured into an appropriate mold, left to harden there and then removed from the mold. The disadvantage here is the design of the shape, since the desired wall thicknesses of the resulting Hollow bodies do not allow fast filling of complicated geometries.

Alternatively, the solidifying mixture can be filled into a mold that is only a cavity is trained. If you let the mixture solidify there, you would get a compact body, no hollow shape. Appropriate process control can ensure that the mixture first solidified on the wall of the mold. If you turn the shape over after a certain time t, then the excess mixture flows off and leaves a lining of the form, which itself is one Represents hollow form, which can be removed from the mold after complete solidification. As already mentioned, can filling also takes place before demolding; also a filling during the Solidification process is possible.  

Preferred embodiments of the present invention are therefore methods in which in step i) an open die form is filled with the flowable shell material and after a time t between 0 and 5 minutes the excess mass is emptied.

As an alternative to completely filling the die mold and pouring off excess mixture the die shape can only be partially filled. In these cases, the mixture is mixed with a suitable stamp pressed against the wall of the die form, where it solidifies into a hollow body. This The process variant essentially represents an intermediate form between the "pouring technique" and the casting technique in negative forms of the hollow body. Corresponding processes in which in step i) an open The mold is filled with the flowable shell material and the material is stamped on the Walls of the mold are pressed and thus a hollow shape is produced, are therefore also preferred. Particularly advantageous in this procedure, which is also referred to as the "cold stamp method" is the possibility, even large quantities with precisely defined wall thickness of the hollow body manufacture. In addition, the process is largely insensitive to fluctuations Flow properties and also applicable for higher viscosity mixtures.

The methods described above are particularly suitable for producing hollow bodies, which have a shape without undercuts, ie have the shape of a "shell", d. H. an opening area which corresponds to the largest horizontal cross-sectional area. These "bowls" can be filled and optionally closed.

With regard to the shape of the shells, the person skilled in the art has no limits in the selection. Of the hemisphere over angular ("cardboard-like") shells to complicated structures with pronounced Surface structures (e.g. in the form of nutshells or animal shapes) are all hollow bodies produced.

According to the invention, however, it is also possible to produce hollow bodies which have only a small opening own and fill the resulting hollow shape later through this small "bunghole". Corresponding processes are mostly on an industrial scale with closable double forms carried out with a sufficient amount for wall lining in the desired thickness solidifying mixture filled and moved in all directions. Here are all Shapes possible, from spheres to egg shapes to complicated hollow structures such as Animal shapes, company logos, etc. Another preferred embodiment of the present invention therefore provides a method in which in step i) a closable double form with the later solidifying mass is filled and moved for a time t between 0 and 5 minutes.

The hollow molds are filled with detergent or cleaning agent during or after production. All ready-made detergents or cleaning agents can be introduced into the hollow mold in liquid, pasty, gel-like, powdered, extruded, granulated, pelletized, flaky or tableted form, reference being made to the explanations in the parent application. However, it is not necessary to fill in a finished detergent or cleaning agent; rather, individual detergent or cleaning agent ingredients or precursors thereof can also be introduced into the hollow body. The substances or classes of substances described in detail in the parent application should be mentioned here as examples of substances or classes of substances:
Powder: bicarbonates, slicates, potash, soda, zeolites, polymers (PEG, maleic acid-polyacrylic acid copolymer salts, citric acid, citrates, sugar, soap, disintegrants and disintegrants, sulfates, phosphates, perborates, carboxymethyl cellulose (CMC), LAS powder ( linear alkylbenzenesulfonates), FAS powder (fatty alcohol sulfates).
Pastes: surfactant pastes (LAS paste, aqueous FAS paste), water glass
Compounds: tower powder (spray agglomerates), LAS compounds, FAS compounds, TAED, percarbonate, enzyme extrudates, crude extrudate, nonionic surfactant compounds.
Liquids: polymer solutions (maleic acid-polyacrylic acid copolymer salts in aqueous solutions), phosphonate solutions (aqueous), perfume oils, enzyme solutions, chlorine bleaching solutions, hydrogen peroxide solutions, cationic surfactant solutions, nonionic surfactants.

The liquids can also be in the form of a gel (due to higher active substance concentrations or by adding thickeners, e.g. B. Tixogel® (Süd-Chemie)). The solids can also be used as solutions or suspensions are processed, the liquids as compounds in bound form.

The examples mentioned above show that one can in the hollow body or in the compartments Hollow body can fill all substances or mixtures of substances mentioned. The liquid and pasty Media (those in the upstream manufacturing stages in the physical states mentioned ), you normally have to dry or absorb onto carrier materials. When filling in Compartments no longer need these assembly levels, which is another advantage of the represents method according to the invention.

After filling, the open hollow mold can be closed. This is with liquid or pasty fillings necessary to prevent the filling from escaping before use. In the case of fillings that remain firmly in the hollow mold, the mold cannot be closed, if desired. Closure can also be done in such cases for aesthetic reasons Reasons.

The optional closing of the hollow form can be done in different ways. For molded articles with a bung hole, this can be closed, for example, by inserting a suitable part become. Open molds in the form of hollow bodies without undercuts can be made with foils sealed or poured over with additional material for the hollow mold after filling. The optional sealing with foils is described below.  

The film that closes the opening (s) of the hollow mold (s) is placed on the surface of the hollow mold applied and firmly attached to it, for example by gluing, partial Melting or chemical reaction. It is possible to slide the film on everyone Apply surfaces of the hollow mold (not just over the opening) and adhere firmly to it connect so that the film is a coating, a "coating" of the entire molded body. Preferred detergent and cleaning agent portions produced according to the invention are, however characterized in that the film does not enclose the entire molded body.

For reasons of process economy and aesthetic impression, it is preferred that the film is applied only in such a way that it fulfills a function, i. H. serves to close the mold.

The sealing film can of course also be a laminate of several different ones composite films, about different compositions of individual Film layers can open the hollow mold at certain times in the washing and Cleaning cycle can be released.

Preferred film materials are the polymers known from the prior art. In particular Preferred foils made of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons and in particular between 10,000 and 100,000 Dalton. With regard to the media, in the washing and cleaning agents usually are introduced, in particular detergent tablets are preferred, in which the film consists of a water-soluble polymer.

Such preferred polymers can be synthetic or natural in origin. Become If polymers on a native or partial basis are used as film material, film materials are made of one or more substances from the group carrageenan, guar, pectin, xanthan, cellulose and their derivatives, starch and their derivatives as well as gelatin preferred.

Carrageenan is a named after the Irish coastal town of Carragheen, educated and similar to Agar extract from North Atlantic red algae, which is one of the florids. That from the Hot water extract of the algae precipitated carrageenan is a colorless to sand-colored powder with Molar masses of 100000-800000 and a sulfate content of approx. 25%, which is very good in warm water is easily soluble. There are three main components in carrageenan: The yellow-forming f- Fraction consists of D-galactose-4-sulfate and 3,6-anhydro - D-galactose, which alternate in 1,3- and 1,4-position are glycosidically linked (in contrast, agar contains 3,6-anhydro - L- galactose). The non-gelling I fraction is from 1,3-glycosidically linked D-galactose-2-sulfate and 1,4-linked D-galactose-2,6-disulfate residues and lightly mixed in cold water soluble. D-galactose-4-sulfate in 1,3-bond and 3,6-anhydro-a-D-galactose-2-suifate in 1,4- Bound i-carrageenan is both water-soluble and gel-forming. Further Garrageenan types are also designated with Greek letters: a, β, γ, µ, ν, ξ, π, ω, χ.  

The type of cations present (K, NH ₄ , Na, Mg, Ca) also influences the solubility of the carrageenans. Semi-synthetic products that contain only one type of ion and can also be used as film materials in the context of the present invention are also called carrag (h) eenate.

The guar which can be used as film material in the context of the present invention, also called guar flour, is an off-white powder which, by grinding the endosperm, was originally endemic in the Indian and Pakistani regions and has meanwhile also been found in other countries, e.g. B. in the south of the USA, cultivated guar bean (Cyamopsis tetragonobolus) belonging to the legume family. The main component of the guar is up to approx. 85% by weight of the dry substance guaran (guar gum, cyamopsis gum); Minor components are proteins, lipids and cellulose. Guaran itself is a polygalactomannan, ie a polysaccharide, the linear chain of which is unsubstituted (see formula I) and substituted in the C ₆ position with a galactose residue (see formula (II)) mannose units in β-D- (1 → 4) link is established.

The ratio of I: II is approximately 2: 1; Contrary to original assumptions, the II units are not strictly alternating, but are arranged in pairs or triplets in the polygalactomannan molecule. Information on the molar mass of guaran varies significantly with values of approx. 2.2.10 ⁵ -2.2.10 ⁶ g / mol depending on the degree of purity of the polysaccharide - the high value was determined on a highly purified product - and corresponds to approx. 1350-13500 sugar- units / macromolecule. Guaran is insoluble in most organic solvents.

The pectins that can also be used as film material are high-molecular glycosidic plant substances that are very common in fruits, roots and leaves. The pectins consist essentially of chains of 1,4-n-glycoside. connected galacturonic acid units, the acid groups of which are 20-80% esterified with methanol, a distinction being made between highly esterified (<50%) and low-esterified pectins (<50%). The pectins have a sheet structure and are thus in the middle of starch and cellulose molecules. Your macromolecules still contain some glucose, galactose, xylose and arabinose and have weakly acidic properties.

Fruit pectin contains 95%, beet pectin up to 85% galacturonic acid. The molecular weights of the different Pectins vary between 10,000 and 500,000. The structural properties are also strong Degree of polymerization dependent; so form z. B. the fruit pectins in the asbestos-like dried state Fibers, the flax pectins, on the other hand, fine, granular powders.

The pectins are mainly extracted from the inner parts of by extraction with dilute acids Citrus peel, leftovers or beet pulp.

Xanthan can also be used as film material according to the invention. Xanthan is a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million Daltons. Xanthan is formed from a chain with β-1,4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan. Xanthan can be described by the following formula:

The celluloses and their derivatives are also suitable as film materials. 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 derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as cellulose-based film material in the context of the present invention. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl 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. In addition to cellulose and cellulose derivatives, (modified) dextrins, starch and starch derivatives can also be used as film materials.

Suitable nonionic organic film materials 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.

Starch can also be used as a film material. Starch is a homoglycan, the Glucose units are linked α-glycosidically. Strength is different from two components Molecular weight built up: From approx. 20-30% straight-chain amylose (MW. Approx. 50,000-150,000) and 70-80% branched chain amylopectin (MW. Approx. 300,000-2,000,000), besides that are still small Contain quantities of lipids, phosphoric acid and cations. While the amylose due to the binding in 1,4-position long, helical, intertwined chains with about 300-1200 glucose molecules forms, the chain branches through in amylopectin after an average of 25 glucose units 1,6 binding to a knot-like structure with about 1500-12000 molecules of glucose. In addition to pure Starch as film materials in the context of the present invention are also starch derivatives which are obtainable from starch by polymer-analogous reactions. Such chemically modified Starches include, for example, products from esterifications or etherifications in which Hydroxy hydrogen atoms have been substituted. But also strengths in which the hydroxy groups with functional groups that are not bound via an oxygen atom are used as starch derivatives. The starch derivatives group, for example Alkaline starches, carboxymethyl starch (CMS), starch esters and ethers and amino starches.

Among the proteins and modified proteins, gelatin has an outstanding film material Importance. Gelatin is a polypeptide (molecular weight: approx. 15,000- <250,000 g / mol), which is primarily by hydrolysis of the collagen contained in the skin and bones of animals under acid or alkaline conditions is obtained. The amino acid composition of gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on of its provenance. The use of gelatin as a water-soluble shell material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules.

Other polymers which can be used as film materials are synthetic polymers which are preferably water-swellable and / or water-soluble. Such synthetic-based polymers can be "tailor-made" for the desired film permeability during storage and dissolution of the film when used. Particularly preferred film materials are selected from a polymer or polymer mixture, the polymer or at least 50% by weight of the polymer mixture being selected from

• a) water-soluble nonionic polymers from the group of
  • 1. polyvinylpyrrolidones,
  • 2. vinyl pyrrolidone / vinyl ester copolymers,
  • 3. Cellulose ether
• b) water-soluble amphoteric polymers from the group of
  • 1. Alkyl acrylamide / acrylic acid copolymers
  • 2. Alkyl acrylamide / methacrylic acid copolymers
  • 3. Alkyl acrylamide / methyl methacrylic acid copolymers
  • 4. Alkyiacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 5. Alkyl acrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 6. Alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers
  • 7. Alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers
  • 8. Copolymers
    • 1. unsaturated carboxylic acids
    • 2. cationically derivatized unsaturated carboxylic acids
    • 3. optionally further ionic or nonionic monomers
• c) water-soluble zwitterionic polymers from the group of
  • 1. Acrylamidoalkyltrialkylammoniumchlorid / acrylic acid copolymers and their alkali and ammonium salts
  • 2. Acrylamidoalkyltrialkylammoniumchlorid / methacrylic acid copolymers and their alkali and ammonium salts
  • 3. Methacroylethyl betaine / methacrylate copolymers
• d) water-soluble anionic polymers from the group of
  • 1. Vinyl acetate / crotonic acid copolymers
  • 2. Vinyl pyrrolidone / vinyl acrylate copolymers
  • 3. Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers
  • 4. 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
  • 5. grafted and crosslinked copolymers from the copolymerization of
    • 1. at least one monomer of the non-ionic type,
    • 2. at least one monomer of the ionic type,
    • 3. of polyethylene glycol and
    • 4. a networked person
  • 6. copolymers obtained by copolymerizing at least one monomer of each of the following three groups:
    • 1. esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
    • 2. unsaturated carboxylic acids,
    • 3. Esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids of group d6ii) with saturated or unsaturated, straight-chain or branched C _8-18 alcohol
  • 7. Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
  • 8. Tetra and pentapolymers
    • 1. Crotonic acid or allyloxyacetic acid
    • 2. Vinyl acetate or vinyl propionate
    • 3. branched allyl or methallyl esters
    • 4. Vinyl ethers, vinyl term or straight-chain allyl or methallyl esters
  • 9. Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
  • 10. Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic monocarboxylic acid branched in position
• e) water-soluble cationic polymers from the group of
  • 1. quaternized cellulose derivatives
  • 2. Polysiloxanes with quaternary groups
  • 3. cationic guar derivatives
  • 4. polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid
  • 5. Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate
  • 6. Vinyl pyrrolidone-methoimidazolinium chloride copolymers
  • 7. Quaternized polyvinyl alcohol
  • 8. Polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

Water-soluble polymers in the sense of the invention are those polymers which are in at room temperature Water are more than 2.5 wt .-% soluble.  

The films can be made from individual polymers mentioned above However, mixtures or multilayered layer structures made of the polymers can also be used become. The polymers are described in more detail below.

Water-soluble polymers preferred according to the invention are nonionic. Suitable non-ionogenic polymers are, for example:

• - Polyvinylpyrrolidones, such as those sold under the name Luviskol® (BASF) become. Polyvinylpyrrolidones are preferred nonionic polymers in the context of the invention.

Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinone)], abbreviation PVP, are polymers of the general formula (III)

by radical polymerization of 1-vinylpyrrolidone by the solution or Suspension polymerization using radical formers (peroxides, azo compounds) as Initiators are made. The ionic polymerization of the monomer only provides products with low molecular weights. Commercial polyvinylpyrrolidones have molecular weights in the range of 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 called white, hygroscopic powders or as aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and one Variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, Phenols and the like. a.).

• - Vinylpyrrolidone / vinyl ester copolymers, such as those under the trademark Luviskol® (BASF) are sold. Luviskol® VA 64 and Luviskol VA 73, each Vinyl pyrrolidone / vinyl acetate copolymers are particularly preferred nonionic polymers.

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

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

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

• - Cellulose ethers, such as hydroxypropyl cellulose, hydroxyethyl cellulose and Methyl hydroxypropyl cellulose, such as those sold under the trademark Culminal® and Benecel® (AQUALON) are sold.

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

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 produced 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 the cellulose have reacted with the etherification reagent or how many moles of the 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 differing degrees of polymerization. Hydroxyethyl- and -propyfcelluiosen are soluble in cold and hot water as well as 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.

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. Since the corresponding monomer, vinyl alcohol, is not stable in free form, become polyvinyl alcohols via polymer-analogous reactions by hydrolysis, technically in particular but by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (preferably Methanol) in solution. These technical processes also make PVAL accessible contain a predeterminable residual proportion of acetate groups.

Commercial PVALs (e.g. Mowiol® grades from Hoechst) come as white-yellowish powders or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molecular weights of approx. 20,000-100,000 g / mol) and have different degrees of hydrolysis from 98-99 or 87-89 mol%. They are therefore partially saponified polyvinyl acetates with a residual content of acetyl Groups of approx. 1-2 or 11-13 mol%.

The water solubility of PVAL can be increased by post-treatment with aldehydes (acetalization) Complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax reduce and thus adjust to the desired values.

Other polymers suitable according to the invention are water-soluble amphopolymers. Ampho-polymers include amphoteric polymers, ie polymers that contain free amino groups as well as free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, zwitterionic polymers that contain quaternary ammonium groups and - Contain COO ^- or -SO ₃ groups, and summarize those polymers which 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. acrylamido propyl-trimethyl-ammonium chloride) and optionally other ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the prior art cited therein. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, as are commercially available under the name Merquat®2001 N, are particularly preferred amphopolymers according to the invention. Further 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, those in the German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 disclosed polymers. Acrylamidopropyltrimethylammoniumchlorid / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Furthermore suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which under the Name Amersette® (AMERCHOL) are commercially available.

Anionic polymers suitable according to the invention include:

• - VinylacetatlCrotonic acid copolymers, such as those under the names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset® (GAF) are on the market.

In addition to monomer units of the above formula (IV), 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 that under the name Luviflex VBM-35 (BASF) available vinyl pyrrolidone / acrylate terpolymers.
• - Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, for example, under the Name Ultrahold® strong (BASF) are sold.
• - Graft polymers from vinyl esters, esters of acrylic acid or methacrylic acid alone or in Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid Polyalkylene oxides and / or polyalkylene glycols

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or mixed 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, i.e. especially 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, which have already been described in detail as materials for the hollow form.

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 non-ionic monomers can be of very different types and are among them 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 non-ionic monomers can likewise be of very different types, whereby among these particularly preferred 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.

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 wt .-% of a crosslinker, the percentage of the crosslinker by the Ratio of the total weights of i), ii) and iii) is formed.

• copolymers obtained by copolymerization of at least one monomer from each of the following three groups:
  • 1. esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
  • 2. unsaturated carboxylic acids,
  • 3. Esters of long-chain carboxylic acids and unsaturated alcohol 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 are to be understood as meaning those having 1 to 8 carbon atoms, the carbon chains of these compounds being optionally interrupted by double-bonded hetero groups such as -O-, -NH-, -S-.

• Terpolymers of crotonic acid, vinyl acetate and an A 24618 00070 552 001000280000000200012000285912450700040 0002010058647 00004 24499llyl or methallyl ester

These terpolymers contain monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyesters of the formula IX:

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight-chain or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R _{2 is} preferably 7, 6, 5, 4, 3 or 2.

The above-mentioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% Allyl- or Methallyletsre of formula IX.

• - Tetra and pentapolymers
  • a) Crotonic acid or allyloxyacetic acid
  • b) vinyl acetate or vinyl propionate
  • c) branched allyl or methallyl esters
  • d) vinyl ethers, vinyl term or straight-chain allyl or methallyl esters
• Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, Vinylbenzene, vinymethyl ether, acrylamide and their water-soluble salts
• - Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic branched monocarboxylic acid in position.

The anionic polymers in particular include polycarboxylates I as film materials Polycarboxylic acids, polymeric polycarboxylates, polyaspartic acid, polyacetals and dextrins are described below.

Useful organic film materials are, for example, those in the form of their sodium salts polycarboxylic acids which can also be used in free form. Polymeric polycarboxylates are, for example Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass from 500 to 70,000 g / mol.

For the purposes 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), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to Have 20,000 g / mol. Because of their superior solubility, this group can turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferred from 3000 to 5000 g / mol, may be preferred.

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 special 30,000 to 40,000 g / mol.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Biodegradable polymers made of more than are particularly preferred as film materials two different monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or as monomers Contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymeric film materials preferably have acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.  

Likewise, other preferred film materials are polymeric aminodicarboxylic acids and their salts or to name their precursors. Polyaspartic acids or their salts and derivatives.

Other suitable film materials are polyacetals, which by reacting dialdehydes with 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 polymers that can preferably be used as film materials are cationic polymers. Among the cationic polymers, the permanently cationic polymers are preferred. As "permanent According to the invention, cationic polymers are those which are independent of the pH of the By means of (ie both the film and the rest of the detergent tablets) one have cationic group. These are usually polymers that have a quaternary nitrogen atom, for example in the form of an ammonium group.

Preferred cationic polymers are, for example

• - Quaternized cellulose derivatives, such as those under the names Celquat® and Polymer JR® are commercially available. The compounds Celquat® H 100, Celquat® L 200 and polymer JR®400 are preferred quaternized cellulose derivatives.
• - Polysiloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning® 929 Emulsion (containing a hydroxylamino-modified silicone, also known as Amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (Her manufacturer: Wacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary Polydime-thylsiloxanes, Quaternium-80),
• - Cationic guar derivatives, in particular those under the trade names Cosmedia®Guar and Jaguar® distributed products,
• - Polymer Dimethyldiallylammoniumsalze and their copolymers with esters and amides of Acrylic acid and methacrylic acid. The under the names Merquat®100 (Poly (dimethyldiallylammonium chloride)) and Merquat®550 (dimethyldiallylammonium chloride- Acrylamide copolymer) commercially available products are examples of such cationic Polymers.
• - Copolymers of vinyl pyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, such as vinyl pyrrolidone quaternized with diethyl sulfate, Dimethylaminomethacrylate copolymers. Such connections are under the names Gafquat®734 and Gafquat®755 commercially available.
• - Vinylpyrrolidone-methoimidazolinium chloride copolymers as described under the name Luviquat® are offered.  
• - quaternized polyvinyl alcohol

as well as those under the designations

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

known polymers with quaternary nitrogen atoms in the main polymer chain. The polymers mentioned are named according to the so-called INCI nomenclature, with detailed information in the CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^th

Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997, refer to the here expressly Reference is made.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the commercial product Polymer®JR 400 are very particularly preferred cationic Polymers.

Processes according to the invention are independent of the chemical composition of the film preferred, in which the film which is used in step iii) to close the hollow mold, a thickness of 1 to 150 microns, preferably from 2 to 100 microns, particularly preferably from 5 to 75 microns and in particular from 10 to 50 microns.

Due to the division into hollow form and filling, a molded article produced according to the invention comprises two areas in which different ingredients are contained or different Release mechanisms and release kinetics can be realized. The one in the hollow form The active substance contained can be in any physical state or any form of presentation accept. Preferred detergent or cleaning agent portions contain the further active substance in liquid, gel-like, pasty or solid form.

When incorporating liquid, gel-like or pasty active substances or Active substance mixtures, the composition of the hollow body and the film on the filling be adjusted to prevent premature destruction of the film or loss of active substance to avoid through the hollow body. This is when solid substances are incorporated into the Hollow mold required only to a minor extent (chemical incompatibility), so that in preferred manufacturing process, the washing or filled into the mold Detergent composition in particle form, preferably in powder, granular, extruded, pelleted, prilled, flaked or tableted form.  

The hollow mold closed by the film can be completely filled with further active substance his. However, it is also possible to fill up the hollow mold only partially before closing in this way a movement of the filled particles or liquids within the hollow mold enable. Especially when filling with regularly shaped larger particles Realize attractive optical effects. Here are washing or manufactured according to the invention Detergent portions preferred, in which the volume ratio of that through the film and the hollow space enclosed to the active substance contained in this space 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to Is 10: 1. In this terminology, a volume ratio of 1: 1 means that the hollow shape is completely filled out.

Depending on the size of the hollow shape, the density of the hollow body, the density of the Active substance in the hollow form and the degree of filling of the hollow form can be the proportion of the others Make up active substance in the hollow mold different proportions of the total molded body. in this connection portions of detergent or cleaning agent produced according to the invention are preferred in which the Weight ratio of hollow body to that in that enclosed by the film and the hollow body Active substance contained 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1. With the weight ratio defined above is the ratio of the mass of the empty hollow body to the mass of the filling. The The mass of the film is not taken into account in this calculation.

By suitable packaging of the hollow body and film material, the time at which the substances contained in the hollow body are released, predetermined. For example the film is quasi instantly soluble, so that the active substance contained in the hollow mold immediately Metered into the washing or cleaning liquor at the beginning of the washing or cleaning cycle. alternative for this purpose, the film can be so poorly soluble that only the molded body is dissolved and that in the Active substance contained in the hollow form is thereby released.

Depending on this release mechanism, moldings can be produced, for example, in which the active substance contained in the hollow form is dissolved in the cleaning liquor before the components of the hollow body are released or after this has happened. So are on the one hand Detergent tablets are preferred, which are characterized in that the in the active substance contained by the film and the hollow body faster loosens as the hollow body. But also detergent tablets, in which the in the active substance contained by the film and the hollow body more slowly dissolves as the hollow body, are preferred embodiments of the present invention.

As an alternative to sealing with a film, the filled hollow bodies can also be applied a melt, solution, emulsion or dispersion of the above-mentioned film materials be closed. The sealing layer forms from the melt, solution, Emulsion or dispersion by cooling or evaporation of the solvent, d. H. the  sealing "film" is created on the hollow mold. This alternative can be used in particular use fully filled molds while only partially filled molds expediently be closed in a different way, provided that there is a "mobility" of the Content value, for example as a special purchase incentive.

Of course, the hollow bodies can also be produced in step i) in such a way that they are connected to a connected further filled hollow body and can be closed in this way. Such Bodies are made up of two half-shells without undercuts, which are one Own equatorial level. The latter does not necessarily have to be arranged in the center, but can for example in the upper or lower third, fourth, fifth, etc. This The procedure is made easier if the hollow bodies produced in step i) have flange parts. Alternatively, the adhesion of the molded parts to one another can also be achieved only via the boundary edges of the Opening areas take place. Methods are also preferred in which the hollow parts of the flange owns and is sealed in step iii) by welding with another hollow mold.

A complete manufacturing process is shown below using the example of a melt Starting material for the hollow mold explained - of course, all other of the Apply the aforementioned solidification mechanisms completely analogously. In a first preliminary stage the molded shell material is melted in a storage container and onto the required one Casting temperature tempered, which can optionally be pre-crystallized. The melt is then fed to the dosing stations via heated and / or insulated line systems; parallel For this purpose, the individual casting molds are preheated or cooled to the desired temperature.

In a casting machine, the liquid melt is metered into the mold troughs, which are up to to the top of the die. As a rule, several identical molds are started past the casting machine and are filled. After leaving the casting machine (or the Passing the dosing head), the filled molds are either fed to a cooling section or keep moving or "parked" until the melt begins to solidify from the outside. Essential for that The later wall thickness of the molded shell to be formed is, among other things, the substance-dependent one Cooling time.

After the specified time, the shape is turned once from the top down or turned upside down so that the not yet solidified and excess melt mass from the mold in a waiting collection reservoir for recycling in the process. Depending on the fabric system and in particular in the case of slowly solidifying melts there is still none at the time of emptying fully solidified shell, so that mainly the adhesion to the mold for the Remains of the enamel in the mold ensures. Adhesive shell formation can be caused by a Eccentric movement of the mold are supported, with the centrifugal forces still flowing Transport the melt evenly to the mold surface and use it to form a shell ensure even wall thickness. Degassing of the melt by vibration of the mold may be necessary.  

After this, the formation of the shell can be completed by cooling. Possibly Shell residue protruding over the edge of the casting mold can be cut off, using knives or thermal rollers can be used.

The formed shell is then filled and the filling is later cooled if necessary. Depending on the desired type of closing, the shape becomes complete or only partial filled. A sealing barrier layer can be applied to close the mold (especially with liquid fillings), which consists of a substance that has a deeper one Has melting point as the shell material and can be sprayed well. The tight closure the mold can then be filled with the melt for by filling the molded shell the shell material. For even lid formation and for any necessary Degassing can cause the mold to vibrate again during the solidification time. The Solidification to the finished molded body can also occur here by passing through a cooling section be promoted.

Finally, the moldings are removed from the mold in a mold emptying station. This is done from above turned downwards so that the formed body can fall down onto a conveyor belt or is filed. This removal from the mold can be done by twisting or twisting the mold Blow on the back are supported.

As already mentioned, the moldings produced according to the invention can be in any shape and Size are manufactured and combine a high aesthetic appeal with great technical Flexibility and the possibility of different product advantages such as controlled-release To realize concepts.

Another object of the present invention are portioned detergents or cleaning agents with a detergent or cleaning composition, which at least partially from solidified material and is characterized in that the enclosure has a wall thickness 100 up to 6000 µm and consists of a material that is delayed by time Water retention, by cooling below the melting point, by evaporation of solvents, by crystallization, by chemical reaction (s), in particular polymerization, by change the rheological properties e.g. B. by changing shear, by sintering or by means Radiation curing, especially by UV, alpha, beta or gamma rays.

The mechanisms by which the formation of the hollow form can take place have been discussed above described in detail. These statements also apply to the scope of the invention Detergents or cleaning agents. The term "at least partially includes solidified material" indicates that at least part of the surface of the washing or Detergent composition of solidified material in the sense of the above Definition is included. The part not covered by solidified material can either be done in another way  be included (e.g. covered with foil, see above) or have direct contact with the atmosphere. There after the manufacturing process described above, the washing or Detergent composition is filled into a mold, are here according to the invention portioned washing or cleaning agents preferred, in which the containment is at least 50%, preferably at least 60%, particularly preferably at least 70% and in particular at least 80% of the surface of the portioned agent covered.

Similar statements can also be made about the masses, the encompassing and the encompassing take in. Portioned washing or cleaning agents are preferred, in which the ratio the masses of content and content in the range from 10: 1 to 1: 1000, preferably from 2: 1 to 1: 100, particularly preferably from 1: 1 to 1:50 and in particular from 1: 5 to 1:25.

As mentioned above, melts are particularly suitable. Even with the invention portioned detergents or cleaning agents are therefore preferred in which the Enclosure consists of a material whose melting point is in the range of 40 to 250 ° C.

Even with the portioned detergents or cleaning agents, certain substances are detailed above have been described as particularly suitable. Within the scope of the present invention preferred portioned washing or cleaning agents are characterized in that the Include one or more substances from the groups of dicarboxylic acids, Dicarboxylic anhydrides, hydrogen carbonates, hydrogen sulfates and / or urea in amounts of at least 40% by weight, preferably at least 60% by weight and in particular at least Contains 80 wt .-%, each based on the mass of the enclosure.

The washing or at least partially included in the enclosure Detergent composition can be in any form as described in detail above available. Portioned detergents or cleaning agents in which the included detergent or Detergent composition in liquid, pasty, gel-like or particulate form or is in the form of a suspension or emulsion and is completely enclosed by the enclosure are a further preferred embodiment of the present invention.  

Examples 1. Manufacture of hollow balls with bunghole

In a closable double mold made of thematic plastic (Makrolon®), in which the upper and lower shells each had the shape of a hemisphere (radius = 1 cm), 3 g of the substances listed below were metered in in molten form and the mold in the closed state swiveled in all directions for a minute and rotated in space. After demolding, spherical hollow bodies with wall thicknesses between 700 and 1000 μm were obtained, which could be filled with detergent or cleaning agent through a bunghole.

2. Manufacture of hemispheres

Coated aluminum molds with ejector stamps were filled to the top with the melts listed in the table below and, after a certain dwell time, the non-solidified liquid was removed by rotating the mold by 180 °. The hemispherical hollow bodies were then removed from the mold and stored temporarily for further processing. At the same time, the solubility of the shaped bodies was investigated by placing the hemispheres in a 2 liter beaker filled with one liter of distilled water at 25 ° C. and agitated at 60 rpm using a magnetic stirrer. The results of these tests are shown in the table below:

The hemispheres were filled with a detergent composition as an example and sealed. The detergent composition had the following composition:

The filled hollow bodies were covered with a polyvinyl alcohol film (type M8630, Greensol) locked.

The portions according to the invention were characterized by a firm bond between the film and Hollow body, so that no loss of active substance could occur.

Claims (20)

1. A method for producing portioned detergents or cleaning agents, comprising the steps:

• a) production of an open hollow mold by solidification;
• b) filling the hollow mold with detergent or cleaning agent;
• c) optionally closing the mold.

2. The method according to claim 1, characterized in that the open hollow shape by time delayed water binding, by cooling below the melting point, by evaporation of Solvents, by crystallization, by chemical reaction (s), in particular Polymerization, by changing the rheological properties e.g. B. by changed Shear, by sintering or by radiation hardening, especially by UV, alpha beta or gamma rays is produced. 3. The method according to any one of claims 1 or 2, characterized in that steps i) and ii) be carried out simultaneously. 4. The method according to any one of claims 1 or 2, characterized in that steps i) and ii) be carried out one after the other. 5. The method according to any one of claims 1 to 4, characterized in that the manufacture of the open hollow form in step i) by solidifying a melt, the melt being made consists of a material whose melting point is in the range from 40 to 1000 ° C., preferably from 42.5 to 500 ° C, particularly preferably from 45 to 200 ° C and in particular from 50 to 160 ° C. 6. The method according to any one of claims 1 to 4, characterized in that the manufacture of the open hollow form in step i) by delayed water binding, the solidifying mass based on its weight 10 to 95 wt .-%, preferably 15 to 90 wt .-%, particularly preferably 20 to 85% by weight and in particular 25 to 80% by weight of anhydrous substances contains, which harden through hydration. 7. The method according to any one of claims 1 to 4, characterized in that the manufacture of the open mold in step i) by evaporation of solvents, the solidifying mass based on its weight 1 to 50 wt .-%, preferably 2 to 40 wt .-% and contains in particular 5 to 30 wt .-% evaporable solvent. 8. The method according to any one of claims 1 to 4, characterized in that the production of open mold in step i) by sintering, the flowable mixture through Exposure to temperature or chemical reaction is solidified.   9. The method according to any one of claims 1 to 8, characterized in that in step i) manufactured hollow form wall thicknesses from 100 to 6000 µm, preferably from 120 to 4000 µm, particularly preferably from 150 to 3000 μm and in particular from 200 to 2500 μm, wall thicknesses below 2000 μm are preferred. 10. The method according to any one of claims 1 to 9, characterized in that in step i) a open die form filled with the flowable shell material and after a time t between 0 and 5 minutes the excess mass is emptied. 11. The method according to any one of claims 1 to 9, characterized in that in step i) open die form filled with the flowable shell material and the material through a Stamp pressed against the walls of the mold and so a hollow shape is made. 12. The method according to any one of claims 1 to 9, characterized in that in step i) closable double mold filled with the later solidifying mass and for a time t between 0 and 5 minutes. 13. The method according to any one of claims 5 or 9 to 12, characterized in that the melt in step i) one or more substances from the groups of the carboxylic acids, Carboxylic anhydrides, dicarboxylic acids, dicarboxylic anhydrides, hydrogen carbonates, Hydrogen sulfates, polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or Urea in amounts of at least 40% by weight, preferably at least 60% by weight and contains in particular at least 80% by weight, based in each case on the melt. 14. The method according to any one of claims 1 to 13, characterized in that the hollow form Has flange parts and in step iii) by welding to a further hollow shape is closed. 15. Portioned washing or cleaning agent with a washing or cleaning agent composition, which is at least partially comprised of solidified material, thereby characterized in that the enclosure has a wall thickness of 100 to 6000 microns and from a Material exists, which is due to time-delayed water binding, by cooling under the Melting point, by evaporation of solvents, by crystallization, by chemical Recation (s), especially polymerization, by changing the rheological properties z. B. by changed shear, by sintering or by means of radiation curing, in particular was produced by UV, alpha beta or gamma rays. 16. Portioned detergent or cleaning agent according to claim 15, characterized in that the Enclosure consists of a material whose melting point is in the range of 40 to 250 ° C.   17. Portioned detergent or cleaning agent according to one of claims 15 or 16, characterized characterized in that the coverage at least 50%, preferably at least 60%, especially preferably at least 70% and in particular at least 80% of the surface of the portioned Covered by means. 18. Portioned detergent or cleaning agent according to one of claims 16 or 17, characterized characterized in that the enclosure one or more substances from the groups of Dicarboxylic acids, dicarboxylic acid anhydrides, hydrogen carbonates, hydrogen sulfates and / or Urea in amounts of at least 40% by weight, preferably at least 60% by weight and contains in particular at least 80% by weight, in each case based on the mass of the enclosure. 19. Portioned detergent or cleaning agent according to one of claims 15 to 18, characterized characterized in that the detergent or cleaning composition included in liquid, pasty, gel-like or particulate form or in the form of a suspension or emulsion is present and is completely included in the scope. 20. Portioned detergent or cleaning agent according to one of claims 15 to 19, characterized characterized in that the ratio of masses of containment and content is in the range of 10: 1 to 1: 1000, preferably from 2: 1 to 1: 100, particularly preferably from 1: 1 to 1:50 and in particular from 1: 5 to 1:25.