DE10051566A1 - Rapidly dissolving, calcium deposit-preventing detergent bodies (e.g tablets) contain room temperature solid (e.g amidosulfonic or polyacrylic) acid of specified average diameter - Google Patents

Abstract

A detergent or cleaning agent solid body containing a room temperature solid acid, optionally together with other ingredients, is such that the average diameter (d50) of the acid particles is 0.01-0.2mm.

Description

The present invention relates to an acidic molding, in particular a washing and Detergent tablets containing an acid present in solid form at room temperature and optionally other components.

Detergent tablets include detergent tablets for the Washing of textiles, detergent tablets for machine or manual Dishwashing or cleaning hard surfaces, bleach tablets for use in Washing machines or dishwashers, water softening tablets, tablets for removal of limescale, stain remover tablets or toilet cleaning tablets. such Shaped bodies are well known in the prior art and are popular with consumers because of the simple dosing increasing popularity. You have powdered versus liquid products have a number of advantages: they are easier to dose and to handle and due to their compact structure have advantages in storage and transport.

A variety of known moldings contain u. a. Acids as active substances. The selection of acids for use in moldings is due to the compounds present in solid form limited.

An important property of detergent tablets is their release speed and the distribution of the active substances. For faster resolution and distribution of the active substances, such agents preferably contain sodium carbonate and / or Sodium bicarbonate as a sparkling component.

In particular in the case of moldings which are used as so-called machine care products be, e.g. B. decalcifying agent or water softener, it is preferred if it is very dissolve quickly and the active substances are released immediately.

However, the acids present in solid form often have the disadvantage that after the Compress into molded articles using so-called tableting aids short storage times are no longer soluble.

There is a constant need to increase the effectiveness of detergent tablets increase and also improve their manageability.

The object of the present invention was to provide detergent tablets for To provide, which have a good effectiveness and which, even after a long time  Storage time, dissolve quickly and residue-free in water and to prevent Limescale deposits or limescale removal can be used.

The present invention accordingly relates to acidic washing and cleaning agents molded article containing at least one in solid form at room temperature lying acid, optionally in a mixture with other components, characterized in that that the average particle diameter (d50) of the solid acid particles is between 0.01 and 0.2, is preferably between 0.01 and 0.1 mm.

Surprisingly, it was found that detergent tablets, which act as a Active substance an acid present in solid form at room temperature, the one has an average particle diameter (d50) which is between 0.01 and 0.2, preferably between 0.01 and 0.1 mm lies, show a very good dissolving behavior and good prevention of Lime deposits and / or suitable for limescale removal.

Another object of the present invention is accordingly the use of washing and detergent tablets containing at least one in solid form at room temperature acid present, the mean particle diameter (d50) of the solid acid particles between 0.01 and 0.2, preferably between 0.01 and 0.1 mm, optionally in a mixture with other components to prevent limescale deposits and / or limescale removal.

In a particularly preferred embodiment, the acid present in solid form has one average particle diameter (d50) between 0.01 and 0.03 mm, preferably none Particles are present which have a particle diameter of more than 0.05 mm.

The washing and cleaning agent according to the invention contains an essential component molded body an acid present in solid form at room temperature. It will be preferred selected those acids that are able to remove limescale.

Examples of suitable acids in solid form, the particle diameter of which in the defined range are boric acid and alkali metal hydrogen sulfates, Alkali metal dihydrogen phosphates and other inorganic salts as well as solid mono-, oligo- and Polycarboxylic acids and hydroxycarboxylic acids, such as citric acid, malic acid, tartaric acid, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well Polyacrylic acid, organic sulfonic acids such as amidosulfonic acid and any mixtures of this. Commercially available and also as an acid in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture of succinic acid, is preferred (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight). In a preferred embodiment, amidosulfonic acid is used as the solid acid.  

The moldings according to the invention preferably contain one or more acids, one has or have average particle diameter in the range defined above, in one Amount of 20 to 80 wt .-%, based on the entire molded body.

It is not necessary that the total amount of acid have a particle size in the above specified range. If several acids are used, some of the acid can also have a larger particle diameter, ie a particle diameter ≧ 0.2 mm. The proportion of acids with a larger particle diameter is preferably not more than 10% by weight, in particular not more than 5% by weight, based on the finished molded article. Related to the acid with a particle diameter <0.2 mm, the further acid with a Particle diameter ≧ 0.2 mm preferably in an amount up to 20 wt .-%.

In addition to the acid present in solid form, the detergent tablets can have further usual ingredients contained in such molded articles. Type and amount of other ingredients are based in the usual way on the intended use of the Molding.

Shaped articles with particularly good dissolving properties are obtained when the invention contained solid acid with a - if the solid acid also have builder properties should - additional builder is mixed, which is essentially the same Particle size distribution as the acid has. The weight ratio of acid to builder is preferably ≧ 1: 1, particularly preferably ≧ 2: 1 and in particular ≧ 10: 1. One particularly good solubility is achieved when acid and builder in a weight ratio of 20: 1 up to 10: 1 can be used. Builders used with particular preference are phosphates, especially tripolyphosphate (TPP), to be described later.

The other ingredients fulfill one or more primary functions and / or one or more Secondary functions. The primary functions serve the actual cleaning or Washing effect of the cleaning and detergent tablets and its application side Manageability, for example the disintegration properties. The secondary functions are used to manufacture the cleaning and detergent tablets and its Manageability on the provision side, for example the breaking strength. Other ingredients with Secondary functions are also referred to as tableting aids or tablet aids. A clear separation into other ingredients with pure primary function and those with pure Secondary function is not always possible, since primary and secondary functions are often the same be fulfilled. In particular, the other ingredients with secondary function can possibly have several Unite properties.

Due to their primary function, important additional ingredients are disintegration aids, Surfactants, bleaches and builders as well as corrosion inhibitors, soil release compounds, Enzymes, complexing agents, soil repellents, optical brighteners, colors and fragrances as well  anti-microbial agents. Because of their secondary function, there are other important ingredients Fillers, release agents or lubricants, binders and powdering agents. These other ingredients are described below.

It will be no problem for the person skilled in the art to understand the individual components and their amounts depend on the intended use of the cleaning and washing to select medium shaped bodies. For example, a universal detergent tablet will be higher Amounts of surfactant (s) included while using a bleach tablet on their use may even be dispensed with entirely.

disintegration aid

It is to facilitate the disintegration of highly compressed detergent tablets possible to incorporate disintegration aids, so-called tablet disintegrants, in order to to shorten the disintegration times. Under tablet disintegrants or disintegrators according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical Technologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances which are necessary for the rapid disintegration of Tablets in water or gastric juice and for the release of pharmaceuticals in absorbable form to care.

These substances, which are also called "explosives" due to their effectiveness, enlarge their volume in the event of water ingress, on the one hand increasing their own volume (swelling), on the other hand, a pressure can be generated via the release of gases, which the Tablet breaks into smaller particles. As disintegration promoting systems are in Detergent tablets are often also used as so-called "shower systems". On The well-known shower system is carbonate / citric acid systems. overflowing Disintegration aids include synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, Alginates or casein derivatives.

shower systems

A shower system consists of a combination of two or more substances that are used in What release a gas such as carbon dioxide or oxygen. Preferred shower systems consist of one or more acidic components and one or more coal di oxide sources.

Suitable acidic components are, for example, organic acids, in particular - optionally hydroxyl-bearing - oligocarboxylic acids such as di- and tricarboxylic acids, for example succinic acid, maleic acid, glutaric acid, adipic acid, tartaric acid and in particular citric acid, and acidic salts of polyvalent inorganic or organic acids, e.g. As potassium dihydrogen phosphate or sodium bisulfate, and amidosulfuric acid (H ₂ N-SO ₂ -OH; obsolete: amidosulfonic acid, sulfamic or sulfamic acid), including those that are anyway contained in the moldings according to the invention. Particularly suitable as CO ₂ -releasing components are the salts of carbonic acid, ie carbonates and hydrogen carbonates, and also their mixtures, which are used above all as alkali metal and alkaline earth metal salts.

Particularly preferred acidic components are amidosulfuric acid, citric acid and Sodium hydrogen sulfate and mixtures thereof. Preferred mixtures consist of Amidosulfuric acid and citric acid, preferably in an amido weight ratio sulfuric acid to citric acid from 100 to 1 to 1 to 100, in particular from 50 to 1 to 1 to 20, particularly preferably from 20 to 1 to 1 to 10, extremely preferably from 13 to 1 to 10 to 1 or from 2 to 1 to 1 to 2, for example 12 to 1 or 11 to 1 or 1 to 1. The mixtures of Amidosulfuric acid and citric acid are preferred as the sole acidic component of the Shower systems used, but can also with sodium bicarbonate and / or one or several other acid components can be combined.

Particularly preferred CO ₂ components are sodium carbonate (soda) and sodium hydrogen carbonate (sodium bicarbonate) and mixtures of sodium carbonate and sodium hydrogen carbonate, in particular sodium carbonate and mixtures of sodium carbonate and sodium hydrogen carbonate. Mixtures of sodium carbonate and sodium bicarbonate usually have a weight ratio of sodium bicarbonate to sodium carbonate of 20 to 1 to 1 to 10, in particular 10 to 1 to 1 to 1, particularly preferably 5 to 1 to 3 to 1, most preferably 5 to 1 to 4 to 1, for example 3.6 to 1, 4.4 to 1 or 4.6 to 1.

The higher the bicarbonate content of the CO ₂ component and / or the total content of acid or CO ₂ component or shower system, the more the shower system usually bubbles or foams and the faster the cleaning and cleaning agent usually decomposes detergent tablets.

When selecting the content of acid and CO ₂ component (s), the pH value must also be taken into account, which should be established when using the cleaning and detergent tablets. Shaped bodies for decalcification or toilet cleaning usually contain an excess of acid to ensure sufficient acidity for the cleaning effect. For a shaped article suitable for manual dishwashing, for example, a 10% strength by weight aqueous solution of the detergent shaped article preferably has a pH of less than 7, in particular from 3 to 6. In contrast, for an all-purpose cleaning tablet, for example, an excess of CO ₂ component can be selected in order to be able to obtain an alkaline cleaning solution which is sufficient for the desired cleaning action, for example a pH in the range from 8 to 11, by dissolving the cleaning and detergent tablet.

The cleaning or detergent tablet usually contains a shower system in one Amount of 1 to 99.9% by weight, preferably 10 to 99% by weight, in particular 20 to 98% by weight.

In a preferred embodiment of the invention, the cleaning or detergent tablet contains an effervescent system in an amount of at least 50% by weight, preferably at least 60% by weight, in particular from 70 to 97% by weight, particularly preferably from 80 to 96% by weight, most preferably from 85 to 95% by weight. Cleaning or detergent tablets according to this preferred embodiment contain high amounts of acid and CO ₂ component and / or an excess of acid or CO ₂ component and are therefore suitable for applications in which strong bubbling or foaming and / or high Acidity or alkalinity is required, especially as flushing toilet cleaning tablets (toilet cleaner tablets) for the acidic cleaning of flushing toilets and as decalcifying tablets (descaling tablets) for acidic decalcification.

A detergent tablet suitable as a manual dishwashing detergent can be used for for example, shower system in an amount of 20 to 70% by weight, preferably 25 to 60% by weight, in particular 28 to 55% by weight.

In embodiments of the present invention which are particularly suitable as detergents and / or machine dishwashing detergents, the cleaning and detergent tablet is not an "effervescent tablet", ie it is free of CO ₂ components, preferably also free of oligomeric oligocarboxylic acids, particularly preferably free of citric acid.

Swelling disintegration aids

Instead of or in addition to a shower system, the cleaning and washing can contain one or more swelling disintegration aids, usually in an amount of 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6% by weight.

The preferred swelling disintegrants used in the context of the present invention are cellulose-based disintegrants, so that preferred cleaning and detergent tablets contain such a cellulose-based disintegrant in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular Contain 4 to 6 wt .-%. 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 molar masses of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The cellulose derivatives mentioned are preferably not used alone as disintegrants Cellulose base used, but used in a mixture with cellulose. The salary of this Mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose is particularly preferably used as the disintegrant based on cellulose, which is free of cellulose derivatives.

The cellulose used as disintegration aid is preferably not in finely divided form used, but before mixing into the premixes to be pressed into a coarser one Form transferred, for example granulated or compacted. Cleaning and Detergent tablets, the disintegrants in granular or optionally cogranulated form included, are in the German patent applications DE 197 09 991 and DE 197 10 254 and the international patent application WO 98/40463. These writings are too details on the production of granulated, compacted or cogranulated To remove cellulose disintegrant. The particle sizes of such disintegrants are mostly above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90% by weight between 400 and 1200 µm. The above mentioned coarser disintegration aids and described in more detail in the cited documents cellulose-based are preferred in the context of the present invention as Use disintegration aids and in trade, for example under the name Arbocel® TF-30-HG available from Rettenmaier.

As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial Hydrolysis of celluloses obtained under conditions that only the amorphous areas (approx. Attack 30% of the total cellulose mass) of the celluloses and completely dissolve that leave crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the The microfine celluloses produced by the hydrolysis provide the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm and, for example, granules with a average particle size of 200 microns are compactible.

As part of a special, especially as a detergent and / or machine tableware Detergent suitable, embodiment of the present invention preferred cleaning and Detergent tablets contain one or more disintegration aids, preferably one swelling disintegration aid, in particular based on cellulose, preferably in  granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the Tablet weight.

polyalkylene

The moldings according to the invention can be polyal Contain kylene glycols. Polyalkylene glycols (polyglycols, polyglycol ethers; INCI Chemical Class: Polymeric ethers) are known, predominantly linear, e.g. T. but also branched polyethers which are polymers with terminal hydroxyl groups. The polyalkylene glycols with higher molecular weights are polymolecular, i.e. H. they consist of groups of macromolecules with different molecular weights.

According to the invention, polyalkylene glycols are usually used in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, in particular 1 to 7% by weight, particularly preferably 2 to 5 wt .-%, used. The amount contained in the cleaning and detergent tablets Polyalkylene glycols is preferably chosen so that it is in the cleaning and Detergent tablets absorbing amount of water - with more than one through the Amount of water to be absorbed detergent tablets in the corresponding Partial amount of water - is completely soluble. The maximum soluble amount is determined by both Solubility of the polyalkylene glycol in water determined as well as by said amount of water or Subset of water, depending on the application of the cleaning or Detergent tablets depends. Both sizes are known or by simple Attempts to determine.

Linear or branched, in particular linear, polyalkylene glycols of the general formula are preferred according to the invention

HO- [RO] _n -H,

in which R stands for (CH ₂ ) ₂ , CH ₂ CH (CH ₃ ) and / or for (CH ₂ ) ₄ and n for values from 2 to over 100,000 and which can be prepared by ring-opening polymerization of ethylene oxide, propylene oxide and / or tetrahydrofuran are. These are in particular the polyethylene glycols with R = (CH ₂ ) ₂ , the polypropylene glycols with R = CH ₂ CH (CH ₃ ), the polytetrahydrofurans with R = (CH ₂ ) ₄ and the copolymers of ethylene oxide, propylene oxide and / or tetrahydrofuran ,

Polyalkylene glycols preferred in the context of a particular embodiment of the invention have a melting point above that during the manufacture of the cleaning and Detergent tablets prevailing temperature, preferably above a room temperature of about 21 ° C, especially above 23 ° C and particularly preferably of at least 28 ° C. The melting point of homologous homopolymeric polyalkylene glycols decreases in the Usually with increasing molecular weight and narrowing molecular weight distribution. additionally  the melting point of copolymeric polyalkylene glycols generally increases with increasing Proportion of oxygen, for example in the case of copolymers of ethylene oxide and propylene oxide usually with a growing proportion of polyethylene glycol. Finally, the melting point of the Polypropylene glycols usually increase with increasing tacticity (stereoregularity).

polyethylene glycols

Polyethylene glycols (PEG) with an average relative molecular weight are suitable according to the invention from 800 to 100,000, usually 1000 to 80,000, preferably 1500 to 70,000 and especially 2000 to 60,000.

Low molecular weight PEG with molecular weights below 800 are clear, essentially colorless Liquids and therefore less suitable according to the invention. From a molecular weight of around 800 PEG become partially crystalline solids. With increasing molar mass, PEG become over soft waxes with molecular weights from about 1000 to 2000 to hard waxes with molecular weights up to about 20,000 and above. Finally, high molecular weight PEG with molecular weights over 100,000 are hard thermoplastics and therefore less suitable according to the invention.

In a particularly advantageous embodiment of the invention, one or more Polyethylene glycols with a molecular weight of at least 3000, preferably 4000 to 50000, in particular 6,000 to 40,000, particularly preferably 8,000 to 30,000 and extremely preferred 10,000 to 20,000 used. Detergent tablets according to this Embodiments are particularly moisture-stable, with the moisture stability being compared to the cleaning and detergent tablets with polyethylene glycol with a molecular weight of less than 3000 is noticeably improved again.

There are various nomenclatures for polyethylene glycols that lead to confusion can. The specification of the mean relative molecular weight is then technically common to the indication "PEG", so that "PEG 200" is a polyethylene glycol with a relative molar mass of about 190 to about 210.

According to the INCI nomenclature, the abbreviation PEG is provided with a hyphen and follows directly on the hyphen a number that corresponds to the number n in the general formula above, where the multiples of thousands replace the three zeros "000" with the letter "M", for example PEG-7M for a PEG with a molecular weight of 7000.

Commercially available polyethylene glycols with a molecular weight below 3,000 are examples as PEG 800 / PEG-18, PEG-20, PEG 1000, PEG 1200, PEG 1500 / PEG-32, PEG-40, PEG 2000, PEG-55 and PEG-60, the names according to the two nomenclatures for each other Corresponding polyethylene glycols are separated by the "/" sign.  

Commercially available polyethylene glycols with a molecular weight of 3000 to 88000 are for example PEG 3000, PEG 3350 / PEG-75, PEG 4000 / PEG-90, PEG 4500 / PEG-100, PEG 4600, PEG 6000 / PEG-135, PEG 7000, PEG-150, PEG 8000 / PEG-180, PEG 9000 / PEG-200, PEG 10000 / PEG-240, PEG 12000, PEG 14000, PEG 15000 / PEG-350, PEG-400, PEG 20000, PEG 35000, PEG 50000 and PEG-2M, the names according to the two nomenclatures for Corresponding polyethylene glycols separated by the "/" sign are.

The commercially available polyethylene glycols are, for example, under the trade names Carbowax® 8000 (Union Carbide), Emkapol® 6000 and Renex® PEG 3350 (ICI), Lipoxol® (DEA), Polyglykol® E 4500 (Dow), Pluracol® E8000, Pluriol® E12000 and Lutrol® E4000 (BASF) available and the corresponding trade names with other numbers, each of which is the molecular weight of the Polyethylene glycol specified. Sources of supply for the also as cosmetic ingredients The serving according to INCI polyethylene glycols are the International Cosmetic Ingredient Dictionary and Handbook. The Clariant company also sells Polyethylene glycols, e.g. B. PEG 10000 to PEG 35000.

polypropylene glycols

Polypropylene glycols (PPG) are clear, almost colorless over a broad molecular weight range Liquids or amorphous or crystalline solids, the former less according to the invention are suitable. The INCI nomenclature described above is also used to designate Polypropylene glycols used.

Liquid, viscous polyalkylene glycols usually have molecular weights from 250 (PEG-4) to 4000 (PEG-69) whose low molecular weight representatives are miscible with water, while the higher molecular weight PPG are less water soluble. The polypropylene glycols are caused by Ring opening polymerization of propylene oxide. They are as amorphous or stereoregular polymers producible, whereby tacticity (stereoregularity) leads to the preferred crystalline PPG.

According to the invention, the molar masses of the polypropylene glycols are usually in the range from approx. 2000 to 100000, preferably in the range from 4000 to 50,000, in particular from 6000 to 40,000, particularly preferably from 8,000 to 30,000 and extremely preferably from 10,000 to 20,000.

Polypropylene glycols are commonly available as di- and trihydroxy PEG in a wide range of molecular weights area available. The third hydroxy group comes from the polymerization initiator, if For example, glycerin is used as an initiator for polypropylene glycols, three of which Hydroxy groups react during the polymerization and thus lead to branched trihydroxy PEG.  

polytetrahydrofurans

The polytetrahydrofurans (PTHF) are also called tetramethylene glycols, polytetramethylene called glycol ether or polytetramethylene oxides and are by cationic polymerization (Ring opening polymerization) of tetrahydrofuran accessible at temperatures below 83 ° C Polyalkylene.

PTHF are strictly linear polyether diols that are used in industrial processes using rough sulfuric acid or fluorosulfuric acid can be produced as catalysts. The Molar masses of the PTHF, which can reach values of up to several million, are according to the invention usually in the range from about 650 to 100,000, preferably in the range from 1000 to 50,000, in particular from 1400 to 30,000, particularly preferably from 2900 to 20,000 and most preferably from 4500 to 10000.

PTHF are common liquids or low-melting solids at room temperature crystalline nature. The consistency of the PTHF changes from oily with increasing molar mass waxy to firm. Amorphous PTHF with molecular weights over 100,000 are rubber-like Products. Partly crystalline PTHF melt at approx. 43 ° C. Low molecular weight PTHF are in water soluble.

Commercially available are, for example, polytetrahydrofurans with molecular weights of 650, 1000, 1400, 2000, 2900 and 4500. The commercially available polytetrahydrofurans are for example under the trade names Polytetrahydrofuran 650 or PolyTHF® 4500 (BASF), Terathane® 2900 or Teracol® 1000 (Du Pont) and Polymeg® 2000 (Quaker Oats) available and the corresponding trade names with other numbers, each of which is the molecular weight of the Polyethylene glycol specified.

copolymers

The copolymers are preferably statistical copolymers and in particular block copolymers of ethylene and propylene oxide, ethylene oxide and tetrahydrofuran, Propylene oxide and tetrahydrofuran or ethylene oxide, propylene oxide and tetrahydrofuran, preferred from ethylene and propylene oxide, particularly preferably to block copolymers of ethylene and Propylene oxide. The molecular weights of the copolymers are usually in the range according to the invention from approximately 2000 to 100000, preferably in the range from 3000 to 50,000, in particular from 4000 to 40,000, particularly preferably from 6,000 to 30,000 and extremely preferably from 8,000 to 20,000.

Statistical copolymers of a ethylene and b propylene oxide units preferred according to the invention are, for example, the following copolymers (molecular weight) designated PEG / PPG-a / b in accordance with the International Cosmetic Ingredient Dictionary and Handbook, where a and b represent mean values:
PEG / PPG-125/30 copolymer (7300), PEG / PPG-150/30 copolymer (8400) and PEG / PPG-300/55 copolymer (16400).

Block copolymers of ethylene and propylene oxide preferred according to the invention satisfy the formula HO (CH ₂ CH ₂ O) _x (CH (CH ₃ ) CH ₂ O) _y (CH ₂ CH ₂ O) _{x '} H, in which x and x' are for mean values from 2 to 130 and z stand for mean values from 15 to 67, and are designated with the international free name Poloxamer, which is also used in the International Cosmetic Ingredient Dictionary and Handbook. Each poloxamer is identified by a three-digit number. The first two digits multiplied by 100 indicate the average molar mass of the polypropylene glycol fraction and the last digit multiplied by 10 the polyethylene glycol fraction in% by weight, which is 10 to 80% by weight, preferably at least 30% by weight, in particular at least 40% by weight, particularly preferably at least 50% by weight, extremely preferably at least 60% by weight, for example 70 or 80% by weight. The poloxamers are prepared in two stages, with propylene oxide initially being added to propylene glycol in a controlled manner and the polypropylene glycol block obtained being surrounded by two polyethylene glycol blocks by subsequent addition of ethylene oxide.

The following types of poloxamer (x, y, x '; Molar mass; z. T. melting point): Poloxamer 185 (19, 30, 19; 3500; 27), Poloxamer 215 (24, 35, 24; 4150; 34), Poloxamer 234 (22, 39, 22; 4200), Poloxamer 284 (21, 47, 21; 4600), Poloxamer 235 (27, 39, 27; 4650; 29), Poloxamer 333 (20, 54, 20; 4900; 30), Poloxamer 108 (46, 16, 46; 4950; 48), Poloxamer 402 (13, 67, 13; 5000; 20), Poloxamer 403 (21, 67, 21; 5750; 31), Poloxamer 334 (31, 54, 31; 5900; 32), Poloxamer 335 (38, 54, 38; 6500; 30), Poloxamer 217 (52, 35, 52; 6600; 48), Poloxamer 237 (62, 39, 62; 7700; 49), Poloxamer 188 (75, 30, 75; 8350; 52), Poloxamer 238 (97, 39, 97; 11400; 54), Poloxamer 407 (98, 67, 98; 12600; 56), Poloxamer 288 (122, 47, 122; 13000; 58) and Poloxamer 338 (128, 54, 128; 14600; 57).

The poloxamers are commercially available under the trade names Pluronic® and Synperonic® PE available, a letter from the group L, P and F and a two or three digit number is adjusted. The last digit is identical to the last digit of the poloxamer nomenclature and give the preceding one or two-digit numbers multiplied by 300 the approximate Molar mass of the polypropylene glycol portion or multiplied by 3 roughly that from the first two Digits of the poloxamer nomenclature number, d. H. correspond to 3, 4, 6, 7, 8, 9, 10 and 12 in that order the two-digit numbers 10, 12, 18, 21, 23, 28, 33 and 40 at the beginning the number according to the poloxamer nomenclature. The letters distinguish liquid (L), pasty (P) and solid (F) poloxamers. For example, the Poloxamer 238 is Pluronic® F 88 and Synperonic® PE F 88 available.

Another class of suitable block copolymers of ethylene oxide and propylene oxide suffice the formula HO (CH (CH ₃ ) CH ₂ O) _y (CH ₂ CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y'H Polyethylene glycol block framed by two polypropylene glycol blocks, while in the case of poloxamers a polypropylene glycol block is framed by two polyethylene glycol blocks. The production is again carried out in two stages, with ethylene oxide initially being added to ethylene glycol in a controlled manner and the polyethylene glycol block obtained being bordered by two polypropylene glycol blocks by subsequent addition of propylene oxide.

These block copolymers, like the poloxamers, are commercially available under the trade name Pluronic® (BASF), each with an alphanumeric code consisting of three digits and between the the second and third digits of the letter R follow. The meaning of the digits is with the Be interpretation within the framework of the poloxamer nomenclature identical. The inserted letter R (for Engl. reverse) indicates the inverted structure compared to the poloxamers. preferred The following Pluconic® types (molecular weight; melting point) are representatives of this class: Pluronic® 17R4 (2650; 18), Pluronic® 22R4 (3350; 24), Pluronic® 25R4 (3600; 25), Pluronic® 31R4 (4150; 24), Pluronic® 25R5 (4250; 30), Pluronic® 10R8 (4550; 46), Pluronic® 17R8 (7000; 53), Pluronic® 25R8 (8550; 54).

For incorporation into the moldings according to the invention, in particular anhydrous polyalky Lenglycols, in particular polyethylene glycols, with a melting point or melting range between 30 and 80 ° C, the melt of which is water-soluble.

surfactants

Preferred detergent tablets also contain one or more surfactants.

To develop the washing performance, the cleaning and washing according to the invention medium-shaped surface-active substances from the group of anionic, nonionic, contain zwitterionic or cationic surfactants, being anionic surfactants economic reasons and because of their range of services are clearly preferred.

The surfactant content of detergent tablets and detergent tablets is usually for manual dishwashing between 10 and 40% by weight, preferably between 12.5 and 30% by weight and in particular between 15 and 25% by weight, while detergent tablets for automatic dishwashing between 0.1 and 10% by weight, preferably between 0.5 and 7.5% by weight and in particular contain between 1 and 5% by weight of surfactants. Shaped body for Cleaning hard surfaces (all-purpose cleaner tablets) can, depending on the design have the aforementioned surfactant contents of up to or above 10% by weight. Toilet cleaner tablets usually contain up to 5% by weight of surfactants, preferably 0.1 to 3% by weight, in particular 0.3 up to 2% by weight, particularly preferably 0.5 to 1% by weight. Bleach tablets and Water softening tablets are usually free of surfactants.  

Anionic surfactants

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

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Taking fatty acid glycerin esters are to be understood as the mono-, di- and triesters as well as their mixtures, as in the case of Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the order esterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. Preferred sulfated Fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 Carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.

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

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of not more than 5% by weight.

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

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

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

In the context of the present invention as a detergent or hand dishwashing detergent tablet executed cleaning and detergent tablets preferably contain anionic surfactants in an amount of 5 to 50% by weight, in particular 7.5 to 40% by weight and particularly preferably 10 up to 20 wt .-%, each based on the weight of the molded body.

When selecting the anionic surfactants that are used in the cleaning and washing according to the invention medium-sized bodies are used, the freedom of formulation is not subject to compliance Framework conditions in the way. The preferred anionic surfactants are Alkylbenzene sulfonates, alkyl sulfates and fatty alcohol sulfates, preferred as Detergent tablets designed, cleaning and detergent tablets 2 to 20 wt .-%, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), in each case based on the weight of the molded body.

Nonionic surfactants

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese patent application JP 581217598 or which are preferably described in accordance with the international patent application WO-A- 90/13533 described methods are prepared.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides which can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.

Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the Polyglycosyl residue is a glucose residue and the alkyl residue is an n-alkyl residue.

The detergent tablets according to the invention can preferably be alkyl polyglyco side contain, with contents of the cleaning and detergent tablets over APG 0.2% by weight, based on the entire molded article, is preferred. Particularly preferred Detergent tablets contain APG in quantities of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-di methylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably no longer than that of ethoxylated fatty alcohols, especially not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

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

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

Quaternary ammonium compounds are to be mentioned in particular as cationic surfactants. before ammonium halides such as alkyltrimethylammonium chlorides and dialkyldimethylammonium are added chloride and trialkylmethyl ammonium chloride, e.g. B. cetyltrimethylammonium chloride, stearyltri methylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, Lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. More fiction The quaternized protein hydrolyzates represent usable cationic surfactants.

Cationic silicone oils such as those commercially available are also suitable according to the invention available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone),  Dow Corning 929 emulsion (containing a hydroxylamino modified Silicon, also known as Amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Vdacker) and Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; di quaternary polydimethylsiloxanes, Quaternium-80).

Alkylamidoamines, especially fatty acid amidoamines such as that under the name Tego Amid®S 18 available stearylamidopropyldimethylamine are characterized by a good con ditioning effect especially due to its good biodegradability.

Quaternary ester compounds are also very readily biodegradable "Esterquats", such as the methylhydroxy sold under the Stepantex® trademark alkyldialkoyloxyalkylammoniummethosulfate.

Han is an example of a quaternary sugar derivative that can be used as a cationic surfactant product Glucquat®100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride ".

In the context of the present invention, detergent tablets are preferred, which contain anionic (s) and nonionic (s) surfactant (s), with application technology advantages from certain quantitative ratios in which the individual surfactant classes are used, can result.

For example, detergent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably is between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.

From an application point of view, it can have advantages if certain classes of surfactants are used some phases of the cleaning and detergent tablets or in the entire cleaning and Detergent tablets, d. H. in all phases, are not included. Another important one Embodiment of the present invention therefore provides that at least one phase of the Detergent tablets are free of non-ionic surfactants.

Conversely, the content of individual phases or the entire cleaning and detergent tablets, d. H. all phases, achieved a positive effect on certain surfactants become. The introduction of the alkyl polyglycosides described above has proven advantageous proven so that cleaning and detergent tablets are preferred, in which at least a phase of the cleaning and detergent tablets contains alkyl polyglycosides.

Similar to nonionic surfactants can also be left out of anionic Surfactants result from individual or all phases of detergent tablets, which are more suitable for certain areas of application. It is therefore within the present invention also cleaning and detergent tablets conceivable in which  At least one phase of the detergent tablets is free from anionic surfactants is.

builders

In addition to the washing-active substances, builders are important ingredients of Reini detergents and detergents, in particular all-purpose cleaners, machine dishwashing detergents and Detergents. In the cleaning and detergent tablets according to the invention all builders commonly used in cleaning and washing agents are contained, in particular, therefore, zeolites, silicates, carbonates or hydrogen carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates as well Phosphonates. The builders mentioned can also be used in surfactant-free cleaning and Detergent tablets are used, so that it is possible according to the invention to and to produce detergent tablets for water softening or as bleach tablets can be used.

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

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used. which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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

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

can be described. The zeolite can be used both as a builder in a granular Compound used, as well as a kind of "powdering" of the whole to be pressed Mixture are used, usually both ways to incorporate the zeolite in the premix can be used. Suitable zeolites have an average particle size of less than 10 µm (volume distribution; measurement method: Coulter Counter) and contain preferably 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course - as already mentioned above - use of the general known phosphates as builder substances possible, provided that such use is not sufficient ecological reasons should be avoided. The sodium salts are particularly suitable Orthophosphate, the pyrophosphate and especially the tripolyphosphate, especially that pentasodium triphosphate commonly known as sodium tripolyphosphate.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, benzene hexacarboxylic acid, sugar acids, e.g. B. gluconic acid, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not permitted for ecological reasons is objectionable, and mixtures of these. Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.

The amount of builders is more common, especially in the absence of a shower system as between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50% by weight. Again, the amount of builders used depends on Intended use, so that bleach tablets have higher amounts of builders can (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), for example as detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).  

Because odorants like the carbonates and hydrogen carbonates as well as a number of carboxylic acids the aforementioned quantities are also able to function as components of a shower system not to be understood cumulatively in the presence of a shower system. Contains the cleaning and Detergent tablets thus a shower system, so the amount of additionally contained Builders usually only up to 20 wt .-%, preferably 0.01 to 15 wt .-%, in particular 0.1 to 10% by weight, very preferably 0.3 to 8% by weight, for example 6% by weight, or is at least no additional builders included.

bleach

Among the compounds which serve as bleaching agents and which provide hydrogen peroxide (H ₂ O ₂ ) in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, irrespective of which other ingredients are contained in the detergent tablets. If cleaning tablets or bleach tablets for machine dishwashing are manufactured, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimoxyhexanoic acid (ε-phthalimidoxythanoic acid) (lo PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamido peradipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxy dicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacassyl acid, diperoxy acid -1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Here, cleaning and detergent tablets according to the invention are preferred, the min at least one oxygen bleaching agent from the group comprising alkali perborates, alkali percarbonates, organic peracids and hydrogen peroxide, in particular from the group comprising Alkali perborates and alkali percarbonates, particularly preferably sodium perborate and / or Sodium percarbonate.  

The detergent tablets according to the invention contain one depending on the application or more bleaches in an amount of usually 0 to 50% by weight, preferably 0.1 up to 30% by weight, in particular 1 to 15% by weight. Bleached tablets such as stain remover tablets naturally contain large amounts of bleach, while detergent and Dishwasher tablets medium bleach and detergent tablets like toilet cleaner tablets, usually only small amounts of bleach of up to 5% by weight, for example 1 or 2 wt .-%, or have no bleach at all.

As a bleach, in particular in cleaning and detergent tablets for the machine Dishwashing, as well as detergent tablets, can also release chlorine or bromine Substances are used. Among the appropriate chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example Trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocya only acid (DICA) and / or its salts with cations such as potassium and sodium into consideration. Hy Dantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin, are just as suitable as hypochlorites and other common bleaches containing chlorine.

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

In addition to the conventional bleach activators or in their place, so-called Bleaching catalysts are incorporated into the cleaning and detergent tablets. at these substances are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo selenium complexes or Carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod Ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

The bleaching performance of bleach-containing cleaning and washing agents is preferred shaped bodies such as detergent tablets, detergent tablets or bleach tablets increased the use of bleach activators. So included cleaning and  In a particular embodiment, detergent tablets have at least one bleach activator, preferably from the group of polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), the N-acylimide, especially N-nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) and / or the bleach enhancer kenden transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the Cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and / or Manganese sulfate.

The detergent tablets according to the invention can, based in each case on the whole molded body, for example between 0.5 and 30 wt .-%, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight of one or more bleach activators or contain bleach catalysts. Depending on the intended use of the cleaning and Detergent tablets can vary these amounts. So are in typical Universal detergent tablets bleach activator contents between 0.5 and 10 wt .-%, preferably between 2 and 8 wt .-% and in particular between 4 and 6 wt .-% usual, while Bleach tablets definitely higher contents, for example between 5 and 30 wt .-%, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight can have. The expert is not restricted in his freedom of formulation and this way, detergent tablets that bleach more or less, Make detergent tablets or bleach tablets by checking the levels Bleach activator and bleach varies.

A particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in cleaning and washing agents. Are accordingly preferred cleaning and detergent tablets, characterized in that as Bleach activator tetraacetylethylenediamine is used in the amounts mentioned above.

complexing

Complexing agents can be considered as further possible ingredients. Preferably uses com Plexing agents are the phosphonates, which also have cobuilder properties. there it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly special Meaning as a cobuilder. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt reacts alkaline (pH 9). As an aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), Diethylene triamine pentamethylene phosphonate (DTPMP) as well as their higher homologues in question. she are preferably in the form of neutral sodium salts, e.g. B. as a hexasodium salt  the EDTMP or as the hepta and octa sodium salt of DTPMP. As a builder HEDP is preferably used from the class of the phosphonates. The aminoalkane phosphonates also have a strong ability to bind heavy metals. Accordingly, especially when the agents also contain bleach, may be preferred, aminoalkanephosphonates, use in particular DTPMP, or mixtures of the phosphonates mentioned use.

corrosion inhibitors

Dishwasher detergent tablets according to the invention can be used to protect the items to be washed or the size Schine corrosion inhibitors contain, especially silver protection in the area of the machine dishwashing have a special meaning. Generally, above all Silver preservatives selected from the group of triazoles, benzotriazoles, Bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complex can be used. Benzotriazole and / or are particularly preferably to be used Alkylaminotriazole. In addition, one often finds active chlorine in cleaner formulations Means that can significantly reduce the corroding of the silver surface. In chlorine-free Cleaners are especially oxygen and nitrogenous organic redox-active Compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these ver classes of compounds. Also salt-like and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. The are preferred here Transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) - Complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and Manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware be used.

Soil release connections

Special ingredients in the cleaning and detergent tablets according to the invention for machine dishwashing or hard surface cleaning can be used, are substances that prevent re-soiling of surfaces and / or Facilitate dirt removal after a single application (so-called "soil release Links").

The soil release compounds which can be used include all known in the prior art Links. Cationic polymers such as, for example, are particularly suitable Hydroxypropyl guar; Copolymers of aminoethyl methacrylate and acrylamide as well as copolymers of dimethyldiallylammonium chloride and acrylamide, polymers with imino  Groups, cationic cellulose derivatives, cationic homo- and / or copolymers (Mo monomer units: quaternized ammonium alkyl methacrylate groups).

The cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with ammonium side groups, especially guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary Ethyleneimine polymers and polyesters and polyamides with quaternary side groups as Soil release connections. Are also exceptionally preferred in the context of this application natural polyuronic acids and related substances, as well as polyampholytes and hydrophobized Polyampholytes, or mixtures of these substances.

enzymes

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus obtained enzymatic effects substances. Proteases of the subtilisin type and in particular proteases which are preferred Bacillus lentus are used. Enzyme mixtures are, for example, from Protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, in particular, however, cellulase-containing mixtures of particular interest. Peroxidases too or oxidases have been found to be suitable in some cases. The enzymes can on Trä be adsorbed and / or embedded in coating substances to prevent them from premature decomposition protect tongue. The proportion of enzymes, enzyme mixtures or enzyme granules in the Detergent tablets according to the invention, in particular in detergent and Dishwasher detergent tablets, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2% by weight.

The most commonly used enzymes include lipases, amylases, cellulases and Proteases. Preferred proteases are e.g. B. BLAP®140 from Biozym, Optimase®-M-440 and Opticlean®-M-250 from Solvay Enzymes; Maxacal®CX and Maxapem® or Esperase® the Gist Brocades or Savinase® from Novo. Particularly suitable cellulases and Lipases are Celluzym® 0.7 T and Lipolase® 30 T from Novo Nordisk. Special use Duramyl® and Termamyl® 60 T and Termamyl® 90 T from Novo are found as amylases, Amylase-LT® from Solvay Enzymes or Maxamyl® P5000 from Gist Brocades. Others too Enzymes can be used.  

Soil repellents

In addition, the cleaning and detergent tablets, in particular detergent and Stain remover moldings, also containing components that make oil and grease washable from textiles (so-called soil repellents). This effect becomes special clearly if a textile is soiled that has already been washed several times with one Detergent according to the invention, which contains this oil and fat-dissolving component, washed has been. The preferred oil- and fat-dissolving components include, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of Methoxyl groups from 15 to 30% by weight and hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether and those from the prior art known polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred from these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Optical brighteners

The cleaning and detergent tablets, in particular detergent tablets, can be used as optical brightener derivatives of diaminostilbenedisulfonic acid or its alkali metal salts contain. Are suitable for. B. Salts of 4,4-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) style ben-2,2'-disulfonic acid or compounds of a similar structure which instead of the morpholino A diethanolamino group, a methylamino group, an anilino group or a 2- Wear methoxyethylamino group. Brighteners of the substituted di phenylstyryle may be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4- chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4- (2-sulfostyryl) diphenyl. Mixtures too the aforementioned brighteners can be used.

The optical brighteners are in the cleaning and washing agents according to the invention molded articles, in particular detergent tablets, in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight, each based on the entire molded body used.

Dyes and fragrances

Dyes and fragrances are the cleaning and detergent tablets according to the invention added to improve the aesthetic impression of the products and the consumer to provide visually and sensory "typical and distinctive" product. As Perfume oils or fragrances can individual fragrance compounds, e.g. B. the synthetic Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate,  Phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count among the ethers for example benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol The hydrocarbons mainly include the terpenes such as limonene and pinene. Prefers however, mixtures of different odoriferous substances are used, which together form a generate an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, patchouly, Rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, Lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, Galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and Sandalwood oil.

The colorant content is usually below 0.1% by weight, in particular below 0.05% by weight, while fragrances up to 2% by weight, in particular 0.1 to 0.5% by weight, of the total Can make out formulation.

The fragrances can be incorporated directly into the agents according to the invention, but they can it may also be advantageous to apply the fragrances to carriers, which adhere the perfume to the Reinforce laundry and through a slower fragrance release for long-lasting fragrance Take care of textiles. Cyclodextrins, for example, have proven useful as such carrier materials, the cyclodextrin-perfume complexes additionally coated with other auxiliaries can be.

To improve the aesthetic impression of the agents according to the invention, they can be approved neten dyes are colored. Preferred dyes, their selection to the expert no difficulty, have a high storage stability and insensitivity compared to the other ingredients of the agents and against light and no pronounced Substantivity towards textile fibers so as not to stain them.

To the aesthetic impression of the detergent tablets according to the invention improve, they can be colored with suitable dyes. Preferred dyes, the selection of which is no problem for the person skilled in the art has a high storage stability and insensitivity to the other ingredients of the agents and to light as well no pronounced substantivity towards textile fibers in order not to dye them.

Preferred for use in the cleaning and detergent tablets according to the invention are all colorants that can be oxidatively destroyed in the washing process, as well as mixtures  the same with suitable blue dyes, so-called blue toners. It has proven to be beneficial Use colorants in water or at room temperature in liquid organic Substances are soluble. For example, anionic colorants, e.g. B. anionic Nitroso. A possible colorant is, for example, naphthol green (Color Index (CI) part 1: Acid Green 1; Part 2: 10020), which as a commercial product, for example as Basacid® Green 970 from from BASF, Ludwigshafen, and mixtures of these with suitable blue ones Dyes. Other colorants are Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blau GLW (CAS 12219-32- 8, CI Acidblue 221), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.

In the case of cleaning and detergent tablets for the treatment of textile surfaces, in particular detergent and stain remover tablets, it must be taken into account when choosing the colorant that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the cleaning or washing agents varies. In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in cleaning or washing agents, however, is typically a few 10 ^-3 to 10 ^-4 wt .-%.

Antimicrobial agents

To the detergent tablets according to the invention with an antimicrobial One or more can have an effect or just to preserve it antimicrobial active ingredients may be present, preferably selected from the groups of alcohols, Aldehydes, antimicrobial acids, carboxylic acid esters, acid amides, phenols, phenol derivatives, Diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, Benzamidines, substituted isothiazoles and hydrogenated isothiazole derivatives such as isothiazolines (Dihydroisothiazoles) and isothiazolidines, phthalimide derivatives, pyridine derivatives, antimicrobial surfactant compounds such as antimicrobial quaternary surfactants Compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4- dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides, for example  Phenoxyethanol, undecylenic acid, salicylic acid, benzoic acid, 2-benzyl-4-chlorophenol, 2,2'- Methylene bis (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) -bis- (1-octanamine) -di hydrochloride and N, N'-bis- (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraaza-tetradecanediimidamide, as, for example, according to H. Wailhäußer in "Practice of Sterilization, Disinfection - Preservation Germ Identification - Industrial Hygiene "(5th ed. - Stuttgart; New York: Thieme, 1995).

The detergent tablets according to the invention preferably contain as anti microbial active ingredient component salicylic acid and / or isothiazoline.

The content of one or more antimicrobial agents is usually 0 to 10% by weight, preferably 0.001 to 5% by weight, in particular 0.01 to 2% by weight, especially before adds 0.05 to 1% by weight, most preferably 0.1 to 0.5% by weight.

fillers

Fillers (fillers, extenders, extenders, INCI bulking agents) are - mostly relatively cheap - often chemically inert solids that are added to increase volume and / or weight or to dilute the other solids, but also often to increase their technical usability improve. Fillers are also used to adjust the sales form and / or the concentration.

Suitable fillers are carbonates, especially calcium carbonate, but also silicates (talc, clay, Mica), silica, calcium and barium sulfate, aluminum hydroxide and cellulose powder or microcrystalline cellulose and lactose, sucrose, mannitol and sorbitol as well as starch and dicalcium phosphate.

A particularly preferred filler is sodium sulfate. Fillers such as sodium sulfate act here also as a means of adjustment, d. H. as an adjuvant to improve production technology Processability, flowability, to prevent clumping and dusting, than Carrier substance and to correct the powder properties.

Also suitable are, for example, the following fillers designated according to INCI, which are in the International Cosmetic Ingredient Dictionary and Handbook are described in more detail: Alumina, Aluminum Silicate, Amylodextrin, Attapulgite, Barley (Hordeum Distichon) Flour, Barley (Hordeum Vulgare) Flour, Bentonite, Betaglucan, Biotite, Calcium Aluminum Borosilicate, Calcium Carbonate, Calcium Caseinate, Calcium Phosphate, Calcium Silicate, Calcium Sodium Borosilicate, Calcium Sulphates, cellulose, chalk, chitin, coconut (Cocos Nucifera) Shell Powder, Colloidal Oatmeal, Corn (Zea Mays) Cob Meal, Corn (Zea Mays) Flour, Corn (Zea Mays) Gluten Protein, Corn (Zea Mays) Meal, croscarmellose, dextran, dextrin, diatomaceous earth, fuller's earth, hectorite, hydrated Silica, hydroxyapatite, hydroxypropyl starch phosphate, isomalt, kaolin, lithium magnesium Silicate, Lithium Magnesium Sodium Silicate, Loess, Magnesium Carbonate, Magnesium Carbonate hydroxides, magnesium silicates, magnesium stearates, magnesium sulfates, magnesium  Tallowate, Magnesium Trisilicate, Microcrystalline Cellulose, Microcrystalline Wax, Montmorillonite, Moroccan Lava Clay, Nylon-6, Nylon-11, Nylon-12, Nylon-66, Oat (Avena Sativa) Bran, Oat (Avena Sativa) Flour, Oat (Avens Sativa) Meal, Peach (Prunus Persica) Pit Powder, Peanut (Arachis Hypogaes) Flour, Pecan (Carya Illinoensis) Shell Powder, Perlite, Polydextrose, Polyethylene, Polyoxymethylene Melamine Urea, Polyoxymethylene Urea, Polypropylene, Potato (Solanum Tu berosum) Starch, PTFE, Pumice, Rayon, Rice (Oryza Sativa) Bran, Rice (Oryza Sativa) Starch, Rye (Seeale Cereale) Flour, Silica, Silica Dimethyl Silylate, Silica Silylate, Silk, Silk Powder, Sodium Hydroxypropyl Starch Phosphate, Sodium Magnesium Silicate, Soybean Flour (Glycine Soy), Sweet Almond (Prunus Amygdalus Dulcis) Meal, Tale, Tin Oxide, Titanium Hydroxide, Trimagnesium Phosphate, Walnut (Juglans Mandshurica) Shell Powder, Walnut (Juglans Regia) Shell Powder, Wheat (Triticum Vulgare) Bran, Wheat (Triticum Vulgare) Flour, Wheat (Triticum Vulgare) Powder, Wheat (Triticum Vulgare) Starch, Wood Powder, Zinc Borosilicate and Zinc Oxides.

binder

Binders (dry binders, INCI binders) impart adhesive properties during and after the Compression of a particulate premix to cleaning and washing according to the invention medium molded bodies. Many liquids, surfactants and polymers can be used as binders become. When selecting the binder, it must be ensured that the effect of the Disintegration aid is not adversely affected.

Lactose, sucrose, mannitol, sorbitol and microcrystalline are suitable as binders Cellulose, starch, dicalcium phosphate, starch, alginates, polyvinylpyrrolidone (PVP) and Carboxymethylcellulose. Binders particularly suitable for granulation are starch, Alginates, polyvinyl pyrrolidone and especially carboxymethyl cellulose.

A particularly preferred binder is polyvinyl pyrrolidone (PVP).

Also suitable are, for example, the following binders designated according to INCI, which in International Cosmetic Ingredient Dictionary and Handbook are described in more detail: Acrylami de / Ammonium Acrylate Copolymer, Acrylamide / Sodium Acrylate Copolymer, Acrylates / Acrylamide Copolymer, Acrylates / Ammonium Methacrylate Copolymer, Acrylstes Copolymer, Acryla tes / dimethicone copolymer, acrylates / dimethylaminoethyl methacrylate copolymer, Acrylates / PVP Copolymer, Acrylates / VA Copolymer, Acrylic Acid / Acrylonitrogens Copolymer, Agar, Algin, Alginic Acid, Ammonium Acrylates / Acrylonitrogens Copolymer, Ammonium Acrylates Copolymer, Ammonium Alginate, Ammonium VA / Acrylates Copolymer, Amylopectin, Beeswax, Behenyl Alcohol, Butylated PVP, Butyl Ester of Ethylene / MA Copolymer, Butyl Ester of PVM / MA Copolymer, calcium caseinate, C1-5 alkyl galactomannan, carboxymethyl hydroxyethyl cellulose, Carboxymethyl hydroxypropyl guar, cellulose acetate propionate carboxylate, cellulose gum, Ceresin, Collodion, Corn (Zea Mays) Flour, Croscarmellose, Dextran, Dextran Sulfate, Dextrin,  Dibutylhexyl IPDI, Didecyltetradecyl IPDI, Diglycereth-7 Malate, Dilinoleic Acid / Ethylenediamine Copolymer, Dioctyldecyl IPDI, Dioctyldodecyl IPDI, Dioctyl IPDI, Distarch Glyceryl Ether, Distarch Phosphates, ethyl cellulose, ethylene / acrylic acid copolymer, ethylene / acrylic acid / VA copolymer, Ethylene / Calcium Acrylate Copolymer, Ethylene / MA Copolymer, Ethylene / Magnesium Acrylate Copolymer, Ethylene / Sodium Acrylate Copolymer, Ethylene / VA Copolymer, Ethyl Ester of PVM / MA Copolymer, gelatin, glyceryl starch, guar (Cyanopsis tetragonoloba) gum, hydroabietyl alcohol, Hydrogenated Japan Wax, Hydrogenated Jojoba Wax, Hydrogenated Microcrystalline Wax, Hydrogenated Rice Bran Wax, Hydrogenated Rosin, Hydroxybutyl Methylcellulose, Hydroxyethyl cellulose, hydroxyethyl ethyl cellulose, hydroxylated lanolin, hydroxypropyl cellulose, Hydroxypropyl guar, hydroxypropyl methyl cellulose, isopropyl ester of PVM / MA copolymer, Isopropylidenediphenol bishydroxypropyl PEG-180, isopropyl isostearate, isopropyl lanolate, Isopropyl laurate, isopropyl linoleate, isopropyl myristate, isopropyl oleate, isopropyl palmitate, Isopropyl stearate, isopropyl tallowate, isostearic acid, isostearyl isostearate, isostearyl myristate, Isostearyl Neopentanoate, Isostearyl Palmitate, Japan (Rhus Succedanea) Wax, Karaya (Sterculia Urens) Gum, Lanolin Alcohol, Lanolin Wax, Lithium Magnesium Silicate, Lithium Stearate, Locust Bean (Ceratonia Siliqua) gum, maltodextrin, mannitol, methoxypolyoxymethylene melamine, Methyl cellulose, methyl ethyl cellulose, microcrystalline wax, montan acid wax, montan wax, Oleostearins, Ouricury Wax, Ozokerite, Pectin, PEG-5M, PEG-7M, PEG-9M, PEG-14M, PEG-20M, PEG-23M, PEG-25M, PEG-45M, PEG-90M, PEG-115M, PEG-160M, PEG-100 / IPDI copolymer, Pentaerythrityl tetraabietate, pentaerythrityl tetrabehenate, pentaerythrityl tetrabenzoate, penta erythrityl tetracocoate, pentaerythrityl tetraisostearate, pentaerythrityl tetralaurate, pentaerythrityl Tetraoctanoates, pentaerythrityl tetraoleates, pentaerythrityl tetrapelargonates, pentaerythrityl Tetrastearates, pentaerythrityl trioleates, piperylene / butenes / pentene copolymer, polyacrylamides, Polyacrylic Acid, Polybutene, Polybutyl Acrylate, Polydipentene, Polyethylacrylate, Polyethylene, Polyisobutenes, Polyurethane-1, Polyvinyl Acetate, Polyvinyl Alcohol, Polyvinyl Butyral, Polyvinyl Laurate, polyvinyl methyl ether, potassium alginate, potassium aluminum polyacrylate, potassium Carrageenan, Potato (Solanum Tuberosum) Starch, PPG-6-Sorbeth-245, PPG-6-Sorbeth-500, Propylene Glycol Alginate, PVM / MA Copolymer, PVP, PVP / Decene Copolymer, PVP / dimethylaminoethyl methacrylate copolymer, PVP / eicosene copolymer, PVP / hexadecenes Copolymer, PVP / VA Copolymer, PVP / VA / Itaconic Acid Copolymer, Rosin, Shellac, Shellac Wax, Sodium Acrylate / Vinyl Alcohol Copolymer, Sodium Acrylates Copolymer, Sodium Acrylates / Acrolein Copolymer, Sodium Acrylates / Acrylonitrogens Copolymer, Sodium Carboxymethyl beta glucan, sodium carboxymethyl dextran, sodium carboxymethyl starch, Sodium carrageenan, sodium cellulose sulfate, sodium C4-12 olefin / maleic acid copolymer, Sodium Magnesium Silicate, Sodium Polyacrylate Starch, Sodium Polymethacrylate, Styrene / MA Copolymer, Synthetic Beeswax, Synthetic Candelilla Wax, Synthetic Carnauba, Synthetic Japan Wax, Synthetic Wax, Tragacanth (Astragalus Gummifer) Gum, Triethoxycaprylylsilane, Trimethoxycaprylylsilane, VA / Crotonates Copolymer, Wheat (Triticum Vulgare) Gluten, Wheat (Triticum Vulgare) Starch and Xanthan Gum.  

dustproofer

Special binders are the dust binders that help prevent dust formation during and after the compression of the particulate premix to give cleaning agents according to the invention and detergent tablets are used.

Preferred dust binders are silicone oils and in particular paraffin oils. One or more Dust binders, especially one or more paraffin oils, are usually used in quantities of not more than 3% by weight, preferably in amounts of 0.02 to 1% by weight, in particular 0.1 to 1 wt .-%, used.

release agent

Release agents are solid or liquid substances that bind the adhesive forces between two reduce the surface (e.g. molded part / mold), d. H. prevent them from sticking together by form an easily separable film on both surfaces (abhesive). General Eigen Parting agents are chemical indifference, good spreading ability and one Processing adapted melting point. Release agents come in the form of dispersions (Emulsions or suspensions), sprays, pastes, powders and permanent, mostly branded Release agent films applied. The latter can be done by spraying, painting or dipping the Shape. The so-called internal release agents represent a special case demoulded goods are mixed in and either on the surface of the molded part (Molding) can accumulate or cause the surface to harden faster, so that there can be no bond between mold wall and molded part.

The main classes of release agents are silicones in the form of oils, oil emulsions in water, Fats and resins, waxes (essentially natural and synthetic paraffins with and without functional groups), metal soaps (metal salts of fatty acids such as calcium, lead, magnesium, Aluminum, zinc stearate), fats, polymers (polyvinyl alcohol, polyester and polyolefins), Fluorocarbons, inorganic release agents in the form of powders (such as silicon dioxide, graphite, talc and mica).

Preferred release agents are the metal soaps or paraffin oils.

Areas of application of release agents are 38818 00070 552 001000280000000200012000285913870700040 0002010051566 00004 38699d as mold release agents in pharmaceutical Industry in the production of tablets and dragées (the stearates and talc used here also act as a lubricant).

Release agents are also shown in special terms such as non-stick agents, lubricants and tape selhilfen.  

lubricant

Lubricants are additives for filled plastic masses (molding compounds) to make the fillers lighter sliding and making the molding compounds easier to deform. There are metal soaps and Suitable siloxane combinations. Metal soaps, wax and paraffin Dispersions, sulfated oils or PE waxes, silicone oils, paraffin oils.

Suitable lubricants are e.g. B. starch, talc and silicon dioxide.

flow aids

Free-flowing aids are all aids that are added in small quantities to powdered or granulated, in particular hygroscopic substances, in order to prevent them from clumping or caking and thus guaranteeing continuous free flow; occasionally one speaks of making flowable or of fluidification. Water-insoluble, water-repellent or moisture-adsorbing powders of kieselguhr, pyrogenic silicas, tricalcium phosphate, calcium silicates, Al ₂ O ₃ , MgO, MgCO ₃ , ZnO, stearates, fatty amines and the like can be used as such pouring aids, also called anti-adhesives, anti-caking agents or fluidizing agents.

metal soaps

Metal soaps are the salts of the metals Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Li, Mg, Mn, Ni, Pb, Sn, Sr, Zn (not Na and K) with higher fatty, resin and naphthenic acids (stearates, palmitates, oleates, Linoleate, Resinate, Laurate, Octanoate, Ricinoleate, 12-Hydroxystearate, Naphthenate, Tallate and the same). The metal soaps melt between 15 and 200 ° C and mostly show colloids Behavior and interface activity. Their solubility in water is low; when exposed to Water usually swells first. The metal soaps, in particular the Ca, Li, Sr, Ba, Pb, Mn and Mg soaps also work in machine cleaning and Manufacture of detergent tablets as a lubricant.

A particularly preferred metal soap is magnesium stearate.

The detergent tablet according to the invention contains one or more Metal soaps, in particular magnesium stearate, in an amount of usually 0 to 10% by weight, preferably 0.1 to 5% by weight, in particular 1 to 3% by weight.

powdering

Before pressing the particulate premix described below into Rei Cleaning and detergent tablets can the premix with finely divided surfaces agents are "powdered". This can affect the nature and physical Properties of both the premix (storage, pressing) and the finished cleaning  and detergent tablets can be advantageous. Fine powdering agents are in the stand well-known in the art, mostly zeolites, silicates or other inorganic salts be used. However, the premix is preferably "powdered" with finely divided zeolite, faujasite type zeolites are preferred. Within the scope of the present invention The term "faujasite-type zeolite" denotes all three zeolites that make up the faujasite subgroup of the zeolite structure group 4 (see Donald W. Breck. "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X are So also zeolite Y and faujasite and mixtures of these compounds can be used, the pure zeolite X is preferred.

Also mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites that do not necessarily have to belong to the zeolite structure group 4, are used as powdering agents can be used, it being advantageous if at least 50% by weight of the powdering agent consists of a zeolite of the faujasite type.

manufacturing

The cleaning and detergent tablets according to the invention are first produced by the dry mixing of the components, which are partially or completely pre-granulated can, and then bringing information, in particular compression to tablets, whereby on conventional methods can be used. For the production of the invention Cleaning and detergent tablets are the premix in a so-called matrix compacted between two stamps into a solid compressed material. This process, which follows Briefly referred to as tableting, is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.

In the simplest case of molded article production by applying pressure to itself Cavity of a press to be compressed mixture - simplified below Direct tableting - the mixture to be tabletted is direct, i.e. H. without previous Granulation pressed. The advantages of this so-called direct tableting are its simple and Cost-effective application, since there are no further process steps and, consequently, none other systems are required. However, these advantages are offset by disadvantages. So a powder mixture that is to be tabletted directly must be sufficiently plastic Have deformability and have good flow properties, furthermore it may be used during the Storage, transport and filling of the die show no tendency towards segregation. If a powder mixture fulfills these three requirements, the molded body is produced preferably by direct tableting. Are these three requirements for one Mixtures of substances, on the other hand, are difficult or impossible to control, so the Direct tableting for the production of moldings according to the invention is preferably not applied, but are based on powdery components ("primary particles") this through suitable processes to secondary particles with a larger particle diameter  agglomerated or granulated. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting. in the Be preferred within a particular embodiment of the present invention Detergent tablets by pressing a particulate premix from at least one surfactant-containing granulate and at least one subsequently mixed obtained powdery component. The surfactant-containing granules can be customary Granulation processes such as mixer and plate granulation, fluid bed granulation, extrusion, pelle tion or compacting. It is there for later cleaning and Detergent tablets are advantageous if the premix to be pressed has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular above 700 g / l, having. Another advantage can be derived from a narrower particle size distribution Surfactant granules result. Within the scope of the present invention, cleaning and Preferred detergent tablets in which the granules have particle sizes between 10 and 4000 μm, preferably between 100 and 2000 microns and in particular between 600 and 1400 microns exhibit. In the context of the present invention, cleaning and detergent tablets are preferred, which consist of a particulate premix, the granular components and subsequently contains powdered substances, the or one of which subsequently admixed powdered components a zeolite of the faujasite type with particle sizes is below 100 µm, preferably below 10 µm and in particular below 5 µm and at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be compressed. The finely divided on Preparation components with the particle sizes mentioned above can do this pressing premix can be added dry. But it is also possible and preferred by adding small amounts of liquid substances to the surface of the coarser particles "Adhere". These powdering processes are widely described in the prior art and the Expert familiar. As liquid components that promote adhesion of the powdering agent are suitable, for example nonionic surfactants or aqueous solutions of surfactants or other cleaning and detergent ingredients are used. As part of the In the present invention, it is preferred as a liquid adhesion promoter between finely divided Powdering agent and the coarse particles of perfume.

The - not, partially or completely granulated - premix is introduced into the die, whereby the filling quantity and thus the weight and shape of the resulting molded body by the Position of the lower punch and the shape of the press tool can be determined. The constant dosing, even with high molding throughputs, is preferably carried out via a volumetric dosage of the premix reached. Touched in the further course of tableting the upper stamp pre-mixes and lowers further towards the lower stamp. at this compression, the particles of the premix are pressed closer together, the Cavity volume within the filling between the stamps decreases continuously. From one  certain position of the upper stamp (and thus from a certain pressure on the Premixing) begins the plastic deformation, in which the particles flow together and make it to the Formation of the molded body comes. Depending on the physical properties of the Premix is also crushed some of the premix particles and it comes with even higher ones Press to sinter the premix. With increasing press speed, i.e. high Throughput quantities, the phase of elastic deformation is shortened more and more, so that the resulting moldings can have more or less large cavities. In the last The tableting step is the finished molded body by the lower punch from the die pushed out and transported away by subsequent transport devices. To this Only the weight of the molded body is finally determined at the time, since the compacts are due to physical processes (stretching, crystallographic effects, cooling etc.) their shape and Can still change size.

Tableting machines

Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, not only the upper stamp becomes Pressure build-up used, also the lower punch moves to the during the pressing process Upper stamp closed while the upper stamp presses down. For small production quantities eccentric tablet presses are preferably used, in which the stamp or stamps on an eccentric disc are attached, which in turn on an axis with a certain Revolving speed is mounted. The movement of this ram is with the way of working comparable to a conventional four-stroke engine. The pressing can be done with an upper and Lower stamps are made, but several stamps can also be attached to one eccentric disc be, the number of die holes being expanded accordingly. The throughputs of Eccentric presses vary from a few hundred to a maximum of 3000 tablets per type Hour.

For larger throughputs, rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available. Each die on the die table is assigned an upper and lower stamp, whereby again the pressure is active only by the upper or lower stamp, but also by both stamps can be built. The matrix table and the stamp move around a common one vertical axis, the stamps with the help of rail-like curved tracks during of the circulation in the positions for filling, compression, plastic deformation and discharge to be brought. Wherever a particularly serious increase or Lowering the stamp is necessary (filling, compacting, ejecting), these will be Curved tracks through additional low-pressure pieces, low-tension rails and lifting tracks supported. The die is filled via a rigidly arranged feed device, the  so-called filling shoe, which is connected to a reservoir for the premix. The Press pressure on the premix is individual via the press paths for upper and lower punches adjustable, the pressure build-up by rolling the stamp shaft heads past adjustable Print rolls happen.

Rotary presses can also be equipped with two filling shoes to increase the throughput the, whereby only a semicircle has to be run through to produce a tablet. to Manufacture of two- and multi-layer molded articles are several filling shoes in a row arranged without the lightly pressed first layer being ejected before further filling becomes. With suitable process control, coated and dot tablets are also possible in this way producible, which have an onion skin-like structure, the in the case of the point tablets Top of the core or core layers is not covered and thus remains visible. Also Rotary centrifugal presses can be equipped with single or multiple tools, so that for example, an outer circle with 50 and an inner circle with 35 holes at the same time Pressing can be used. The throughputs of modern rotary tablet presses are over a million moldings per hour.

Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH presses GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU). Be The HPF 630 hydraulic double-pressure press from the company is particularly suitable LAEIS, D.

dimensional shape

The cleaning and detergent tablets can be in a predetermined spatial shape be made of the right size, and they also consist of several phases, i. H. Layers or on closures or cores and rings or spatial shapes with hollows and hollow filling or insert, also called cavity, can exist. Practically all of them come in useful form manageable configurations into consideration, for example the training as a blackboard, the staff or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact Cylinder pieces with a ratio of height to diameter above 1.

The developers of tablet-shaped products came up with the idea early on about under differently composed areas of the shaped bodies under certain ingredients release defined conditions in the washing or cleaning cycle in order to Improve cleaning success. Here, in addition to those from pharmacy, have sufficed known core / shell tablets and ring / core tablets in particular multilayer  Shaped bodies that are used today for many areas of washing and cleaning or Hygiene are offered.

In a particular embodiment of the invention, there is cleaning and washing medium shaped body from two or more different phases, preferably from two or three Phases, in particular from two phases, in the form of layers and / or inclusions and / or Cores and rings and / or room shapes with troughs and trough filling or insert. The The phases may differ in their composition, for example due to the Separation of incompatible components such as bleach and enzymes and / or different ones Coloring, and / or in their nature, for example pressed and not pressed, e.g. B. melted / poured phase. In a preferred embodiment have as two-phase, in particular two-layer, cleaning and detergent tablets the two phases have a weight ratio of 10 to 1 to 1 to 10, preferably 5 to 1 to 1 to 2, in particular 3 to 1 to 1 to 1.5, for example 2 to 1 or 1 to 1.

The portioned compacts can each be separate individual elements be formed, the predetermined dosage of the detergent and / or detergent equivalent. However, it is also possible to form compacts which have a plurality of them Connect mass units in a compact, in particular by predetermined target break points the easy separability of portioned smaller units is provided. For the Use of textile detergents in machines of the type common in Europe with horizontal arranged mechanics can form the portioned compacts as tablets, in cylindrical or cuboid shape may be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or Rotary presses are suitable devices in particular for the production of such Compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions Detergent dispenser of commercial household washing machines adapted so that the molded body can be metered directly into the induction bowl without metering aid, where they can be found during the Dissolves. It goes without saying that the detergent tablets are also used easily possible via a dosing aid.

Another preferred shaped body that can be produced has a plate-like or sheet-like shape Structure with alternating thick long and thin short segments, so that individual Segments of this "latch" at the predetermined breaking points, which are the short thin segments display, canceled and can be entered into the machine. This principle of "Bar-shaped" shaped detergent can also be used in other geometric shapes, For example, vertical triangles that are only along one side of their sides are interconnected, can be realized.  

Another preferred multi-phase molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "multiphase bolt" at the predetermined breaking points, which are the short display thin segments, can be canceled and entered into the machine. This principle of the "bar-shaped" shaped body detergent can also be used in other geometrical Shapes, for example vertical triangles, only on one side are connected alongside each other, can be realized. Here it comes from optical Establish the triangular base that connects the individual segments as one phase form while the triangle tip forms the second phase. Different staining Both phases are particularly attractive in this embodiment.

But it is also possible that the different components do not form a single tablet be pressed, but that shaped bodies are obtained that have several phases, that is at least have two phases. It is also possible that these different phases have different release speeds. This can be advantageous application properties of the moldings result. If, for example Components are contained in the moldings that have a mutually negative effect, so it is possible to integrate one component in the faster soluble phase and the other Work component into a slower soluble phase so that the first component already has reacted when the second goes into solution. The structure of the individual phase can both done in stacks, with a dissolution process of the inner phase (s) at the edges of the Shaped body already takes place when the outer phases have not yet been completely solved but can also completely encase the inner phase (s) by the further outside lying phase (s) can be achieved, which prevents the early release of Components of the inner phase (e) leads.

In a further preferred embodiment of the invention, a molded body consists of min at least three phases, i.e. two outer and at least one inner phase, at least One of the inner phases contains a peroxy bleach, while the staple one Shaped body the two covering phases and the outermost phases of the shell-shaped shaped body but are free of peroxy bleach. It is also possible to use peroxy bleach and optionally existing bleach activators and / or enzymes spatially in a molded body separate from each other. Such multiphase molded articles have the advantage that they are not only via a detergent dispenser or via a dosing device which is added to the wash liquor will be used; rather, it is also possible in such cases, the molded body into the machine in direct contact with the textiles without being stained Bleach and the like would be feared.

In a further embodiment, the shaped bodies according to the invention have one or more Cavities that can be filled accordingly. As fillings for the cavity come z. B.  a solidifying melt or powder into consideration, the powder using a Coating layer can be attached in the cavity. As ingredients are in the caviar preferably substances are incorporated, which, if necessary, become one when the shaped bodies are used released later or earlier than the ingredients of the sintered molded part can be.

In addition to metering in a melt, one or more can also be preferred in another way pre-made core (s) of any shape, e.g. B. Ball, ellipsoid, lens can be mounted. The assembly can be done by the core in the finished molded article is glued or introduced into the preform before tabletting and connects to it during tableting. The core does not necessarily have to be there be visible on the surface of the molded body. It can also be completely below the Surface or exactly in the center of the sintered molded body.

Furthermore, the core can loosely into the cavity on the surface of the preferably already cured Shaped body inserted and poured over with an adhesive or a melt, for. B. one wax-like substance, such as paraffin, PEG etc., can be fixed.

coating

Similar effects can also be obtained by coating individual components of the pressing cleaning and detergent composition or the entire molded body to reach. For this purpose, the mixtures or bodies to be coated can be coated with, for example aqueous solutions or emulsions or melts are sprayed (spraying on the Coating material) or via the process of melt coating (immersion of the Shaped body in the melt or solution) receive a coating. In preferred Embodiments of the present invention are the cleaning and detergent tablets however, not coated with a coating that covers the entire molded body.

breaking strength

After pressing, the cleaning and detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to

Here σ stands for diametral fracture stress (DFS) in Pa, P. the force in N, which leads to the pressure exerted on the molded body, which breaks the Shaped body, D is the shaped body diameter in meters and t is the height of the Moldings.  

Relative equilibrium moisture

Regardless of the intended use of the moldings, it is preferred according to the invention that the or the cleaning and detergent tablets have a relative equilibrium moisture content of less than 30% at 35 ° C.

The relative equilibrium moisture content of the cleaning and detergent tablets can be determined according to common methods, with the scope of the present investigations The following procedure was chosen: A water-tight 1 liter container with a Lid, which has a closable opening for the introduction of samples, was included filled a total of 300 g detergent tablets and 24 h at a constant 23 ° C held to ensure a constant temperature of the vessel and substance. The Water vapor pressure in the space above the molded bodies can then be checked with a hygrometer (Nygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now every 10 minutes measured until two successive values show no deviation (Gleichgeichtsfeuchtigkeit). The above Hygrometer allows a direct display of the recorded Values in% relative humidity.

packaging

The moldings according to the invention can be used individually or in pairs or more with one Packaging system can be combined. The term "packaging system" characterizes in Within the scope of the present invention, the primary packaging of the moldings, i. H. the Packaging that is in direct contact with the molded body surface on the inside.

The combinations of cleaning and detergent tablets and packaging system can of course in turn in secondary packaging, for example cardboard boxes or trays, be packed, with no further requirements being placed on the secondary packaging must, so that all usual materials and systems can be used here. The Secondary packaging is therefore possible and customary in the context of commercial use, but not necessary.

Moisture vapor transmission rate

The packaging system of the combination of detergent tablets and packaging system preferably has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is at 23 ° C and a relative Equilibrium moisture of 85% is stored. The specified temperature and humidity conditions are the test conditions that are specified in DIN standard 53 122, whereby according to DIN 53 122 minimal deviations are permitted (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. The moisture vapor permeability rate can be determined from the surface of the container which is closed with the material to be tested (permeation surface), the weight gain of the calcium chloride and the exposure time

calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as "relative humidity", is 85% at 23 ° C. when measuring the moisture vapor transmission rate in the context of the present invention. The absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° C is saturated with 14.4 g of water vapor; at a temperature of 11 ° C, saturation is already present with 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air at 17 ° C contains 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) .100 = 83%. If this air is cooled, then the saturation (100% RH) is reached at the so-called dew point (in the example: 14 ° C), ie if it cools further, a precipitate is formed in the form of mist (dew). Hygrometers and psychrometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in the laboratory chambers with humidity control depending on the device type to ± 2% r. Adjust L. exactly. Also about saturated solutions of certain salts form in closed systems at a given Temperature constant and well-defined relative humidity, which on the phase Balance between partial pressure of water, saturated solution and soil body.

In one possible embodiment of the present invention, the cleaning and detergent tablets are provided with a packaging system which has a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is at 23 ° C. and a relative equilibrium humidity of 85% is combined.

Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m ² / day to less than 15 g / m ² / day.

dose

Depending on the design, the packaging system encloses one or more cleaning and detergent tablets. It is preferred according to the invention, either a molded body to be designed in such a way that it comprises an application unit of the cleaning and washing agent, and to pack this molded article individually, or the number of molded articles in one Pack packaging unit, which in total comprises an application unit.

In this context, “to be packed individually” is not to be understood as meaning that the shaped bodies are physically separate packaging must be included, but rather that a molded body Packaging system can be removed without the rest of the Packaging system contained individually packaged moldings can also be unpacked. Such individual packaging represents, for example, that in the examples below described blister packaging. The same applies to the packaging unit with more than one Shaped bodies, which are of course part of a physical network of several Packaging unit, as long as each packaging unit can be opened for itself, while the other packaging units remain closed.

With a nominal dosage of 80 g detergent and detergent, as in the area of detergents Is usual, it is possible according to the invention, a 80 g heavy cleaning and Produce detergent tablets and pack them individually, but it is also according to the invention possible, two 40 g heavy detergent and detergent tablets as one To pack the application unit in a packaging in order to create an inventive one Combination. This principle can of course be extended so that combinations according to the invention also three, four, five or even more cleaning and Detergent tablets can contain in a packaging unit.

Of course, two or more molded articles can be different in one package Have compositions. This way it is possible to have certain components to separate them spatially from each other, for example to avoid stability problems.

Material and shape

The packaging system can consist of a wide variety of materials and any other take larger forms. For economic and lighter reasons Processability is preferred, however, packaging systems in which the Verpac kungsmaterial is light in weight, easy to use and inexpensive.  

In combinations preferred according to the invention, in particular combinations with Reini moldings, the packaging system consists of a body with or several shapes for receiving one or more shaped bodies and one or the Forming sealing and the or the shaped body holding cover. such Packaging systems are also known as blisters. The body is preferably made up transparent or non-transparent plastic film, in particular made of polypropylene, the thickness of which is preferably 200 to 600 μm, in particular 300 to 500 μm, for example 400 μm, is. Usually, a, preferably welded, metal foil serves as the cover, Plastic, metal-coated plastic or paper or wax-coated paper, the Thickness is preferably 60 to 200 microns, in particular 100 to 140 microns, for example 120 microns. The commercially available, especially in the pharmaceutical field are widely suitable as cover films widespread, peel, peel-and-push and push-through foils. Such a packaging system is in the following examples and in EP 0 903 405 A2 (Unilever), to which in this With respect to and the content of which is hereby incorporated into this application, described.

In further combinations preferred according to the invention, in particular combinations with Washing and machine dishwashing detergent tablets, the packaging system consists of one Sack or pouch made of single-layer or laminated paper and / or plastic film. there can the cleaning and detergent tablets unsorted, d. H. as a loose fill, in one Bags can be filled from the materials mentioned. But it is for aesthetic reasons and preferred for sorting the combinations in secondary packaging, the cleaning and Fill detergent tablets individually or in groups in sacks or bags. For individual application units of the cleaning and detergent tablets, which are in one Sack or bag, the term "flow pack" has become common in technology. Such "Flow packs" can then - again preferably sorted - optionally in outer packaging be packed, which underlines the compact form of the molded body. The preferred Sacks or pouches to be used as a packaging system made of single-layer or laminated Paper or plastic film can be designed in a variety of ways, for example as an inflated bag without a central seam or as a bag with a central seam, which through Heat (hot melt), adhesives or tapes are sealed. Single-layer Bag or sack materials are the known papers, which may or may not be impregnated can, as well as plastic films, which can optionally be co-extruded. plastic, which can be used as a packaging system in the context of the present invention, are for example in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf, 1988, page 193. Fig. 111 shown there gives at the same time indications of the water vapor permeability of the materials mentioned. As part of Combinations particularly preferred according to the present invention contain as packaging system  a sack or pouch made of single-layer or laminated plastic film with a thickness of 10 to 200 μm, preferably from 20 to 100 μm and in particular from 25 to 50 μm.

Although it is possible, wax-coated in addition to the films or papers mentioned Papers in the form of cardboard boxes as a packaging system for cleaning and washing To use medium-shaped body, it is preferred in the context of the present invention if the Packaging system does not include boxes made of wax-coated paper.  

Examples 1. Grinding of amidosulfonic acid (ASA) / sodium tripolyphosphate (TPP)

Amidosulfonic acid and sodium tripolyphosphate were ground in a weight ratio of 60: 4. The following grain size distribution of the mixture was set:
<0.05 mm 0% by weight
<= 0.05 mm 100% by weight
average diameter (d50): approx.0.02 mm

2. Preparation of the tableting mixture

64% by weight of ground ASS / TPP mixture
3% by weight citric acid, anhydrous (average diameter <0.5 mm)
8 wt% PEG 1500
25% by weight soda, calc.

The individual components were in a manner known per se in a Lödige plow mixed more charmingly.

3. Tableting

Tablet weight: 15 g
Tablet diameter: 34 mm
Tablet height: 10-11 mm
Pressing force: approx. 60 kN

The tablet was placed in a glass jar with limescale. It dissolved after 1.5 Minutes in 400 ml of water at 20 ° C without residue. The limescale had subsided dissolved in a short time.

Claims (13)

1. Detergent tablets containing at least one acid present in solid form at room temperature, optionally in a mixture with other ingredients, characterized in that the average particle diameter of the acid particles (d50) is between 0.01 and 0.2 mm. 2. Shaped body according to claim 1, characterized in that the average particle diameter knife of the acid particles (d50) between 0.01 and 0.1 mm and in particular between 0.01 and 0.03 mm, in the latter case preferably no acid particles a diameter <0.05 mm are included. 3. Shaped body according to claim 1 or 2, characterized in that the acid is selected from boric acid, alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates, solid mono-, oligo- and polycarboxylic acids and -hydroxycarboxylic acids, such as Citric acid, malic acid, tartaric acid, succinic acid, malonic acid, adipic acid, Maleic acid, fumaric acid, oxalic acid and polyacrylic acid, organic sulfonic acids, such as Amidosulfonic acid and any mixtures thereof. 4. Shaped body according to claim 3, characterized in that the acid is sulfamic acid is included. 5. Shaped body according to one of claims 1 to 4, characterized in that the acid or acids with an average particle diameter (d50) between 0.01 and 0.2 mm, preferably between 0.01 and 0.1, in an amount of 20 to 80 wt .-%, based on the entire molded body, is included. 6. Shaped body according to one of claims 1 to 5, characterized in that another Acid with a particle diameter <0.2 mm in an amount not exceeding 10% by weight, in particular not more than 5% by weight, based on the finished molded article. 7. Shaped body according to one of claims 1 to 5, characterized in that another Acid with a particle diameter ≧ 0.2 mm in an amount of up to 20% by weight, based on the acid with a particle diameter <0.2 mm, is included. 8. Shaped body according to one of claims 1 to 7, characterized in that additional builders are included. 9. Shaped body according to claim 8, characterized in that a combination of solid Acid and builder in a weight ratio of ≧ 1: 1, preferably ≧ 2: 1, especially preferably ≧ 10: 1 and in particular from 20: 1 to 10: 1 is contained.   10. Shaped body according to one of claims 1 to 9, characterized in that as further Ingredients disintegration aids, surfactants, bleaches, corrosion inhibitors, Soil-re lease compounds, enzymes, complexing agents, soil repellents, optical brighteners, color and fragrances, anti-microbial agents, fillers, release agents or lubricants, binders and powdering agents as well as any mixtures of the above are contained. 11. Shaped body according to one of claims 1 to 10, characterized in that it is a or has several phases. 12. Shaped body according to one of claims 1 to 11, characterized in that it is a or has several cavities into which suitable fillings can be introduced. 13. Use of detergent tablets according to one of claims 1 to 12 to prevent limescale deposits and / or limescale removal.