EP0985023A1

EP0985023A1 - Detergent shaped body with enhanced dissolving properties

Info

Publication number: EP0985023A1
Application number: EP98929366A
Authority: EP
Inventors: Sandra Witt; Christian Block; Fred Schambil; Gerhard Blasey; Hans-Friedrich Kruse
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-05-30
Filing date: 1998-05-22
Publication date: 2000-03-15
Anticipated expiration: 2018-05-22
Also published as: CA2289305A1; ATE300606T1; SK163199A3; JP2002500690A; HUP0002750A2; DE19722832A1; PL337017A1; CN1257535A; DE59812964D1; ES2246070T3; EP0985023B1; WO1998054283A1

Abstract

Disintegration problems of detergent and cleaning agent shaped bodies containing an effervescent agent can be solved by additionally applying a water-insoluble disintegration adjuvant which is capable of swelling to said shaped bodies. The shaped bodies consist of a densified particle-shaped detergent and cleaning agent composition and contain 1-10 wt. % of a water-insoluble disintegration adjuvant which is capable of swelling, in addition to 3-60 wt. % of a gas-generating effervescent system.

Description

Shaped detergent tablets with improved dissolving properties "

The present invention is in the field of compact moldings which have washing and cleaning properties. In particular, the invention relates to detergent tablets such as, for example, detergent tablets, dishwasher tablets, stain remover tablets or water softening tablets for use in the home, in particular for machine use.

Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequent delayed disintegration. gration of the shaped body in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process.

The problem of the too long disintegration times of highly compressed moldings is known in particular from the pharmaceutical industry, where certain disintegration aids, so-called tablet disintegrants, have been used for a long time in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt “Textbook of pharmaceutical technology ^' ' (6th edition, 1987, pp. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which ensure the rapid disintegration of tablets in water or gastric juice and the release of pharmaceuticals in resorbable form.

"Hager's Handbook of Pharmaceutical Practice '''(5th edition, 1991, p. 942) divides the disintegration accelerators or disintegrants into different classes of substances according to their mechanism of action, the most important disintegration mechanisms being the swelling mechanism, the deformation mechanism ("Deformation"), the wick mechanism ("wicking"), the rejection mechanism ("repulsion") and the development of gas bubbles when in contact with water (effervescent tablets). In the swelling mechanism, the particles swell through the water to be added and increase their volume. This causes local stresses that extend across the entire tablet and thus lead to the disintegration of the compacted structure. The deformation mechanism differs from the swelling mechanism in that the swelling particles were previously compressed by the compression during tableting and now return to their original size when water enters. In the wick mechanism, water is sucked into the interior of the molded body through the disintegration accelerator and thereby loosens the binding forces between the particles, which also leads to the disintegration of the molded body. The repulsion mechanism also differs from this in that the particles released by the water sucked into the pores repel each other by the resulting electrical forces. A fundamentally different mechanism is based on the "effervescent tablets", which contain active substances or active substance systems which, when in contact with water, release gaseous substances which cause the shaped body to burst. Additionally there is the use of hydrophilizing agents which ensure better wetting of the compressed particles in water and thus faster disintegration is known.

While substances that act according to the latter two mechanisms can easily be differentiated from other decay mechanisms, the effects on which the swelling and deformation mechanism as well as the wick and repulsion mechanism are based cannot always be clearly separated from one another, which is why, for practical reasons, a division into hydrophilizing agents, gas-releasing systems and swelling disintegrants makes more sense.

The use of these different disintegrants alone or in combination with one another is well known from pharmaceutical applications. For example, EP-B-0 396 335 (Beecham Group PLC) discloses chewable tablets which, in addition to 1 to 30% by weight of a effervescent system, contain 0.5 to 20% by weight of lemon, wine, adipine and fumarate - or maleic acid and 0.5 to 30% by weight Na, K or Ca (hydrogen) carbonate or Na glycine carbonate additionally 5 to 30% by weight of a disintegrant such as (modified) cellulose, polyvinylpyrrolidone or starch contain keglycolate. The advantage of these chewable tablets, according to the information in the publication, is that the application is more pleasant for the patient and that they feel more comfortable while taking them.

Combinations of effervescent granules and swelling disintegrants are also known from JP 06 024 959 (BAYER YAKUHIN KK, Derwent Abstract). It describes pharmaceutical compositions in tablet form, the active ingredients being mixed with a disintegrator (methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone) and in some cases with disintegrants which contain a swelling, gel-forming polymer (sodium alginate, carrageenan, polyethylene oxide) and a CO ₂ -generating agent Bubble system included, covered. Despite the use of two disintegration systems, these tablets are advertised as active ingredient carriers with delayed release.

The proposed solutions lead to the desired success in the manufacture of pharmaceutical tablets. In the area of detergents and cleaning agents, they contribute to a improvement of the disintegration properties of washing or cleaning tablets; however, the improvement achieved is not sufficient in many cases. This applies in particular if the proportion of sticky organic substances in the tablets, for example anionic and / or nonionic surfactants, increases. In addition, the use of disintegrants in washing and cleaning-active moldings can lead to specific problems that are completely unknown to medicinal products.

For example, the use of a effervescent system in detergent tablets does not lead to the desired rapid disintegration; rather, the effervescence and disintegration effect known from conventional effervescent tablets initially sets in, but comes to a standstill again after a short time, and the tablet is then no longer broken down. Apparently, the above-mentioned detergent and cleaning agent ingredients form a water-impermeable layer after a short time, which prevents the water from penetrating into the tablet and thus preventing it from disintegrating.

Accordingly, for example, the European patent application EP-A-0 466 484 (Unilever) describes tablets made of compressed particulate detergent, which, in addition to surfactant (s) and builder (s), optionally contain further detergent ingredients, with swelling agents preferred in the case of a binder / disintegrant content are.

Detergent and cleaning agent effervescent tablets are described in DE 35 35 516 (Bucher). These tablets contain 2 to 6% by weight of a surfactant, 40 to 60% by weight of hydrogen carbonate, 33 to 53% by weight of a solid organic acid (in particular a 2: 3 mixture of citric and tartaric acid), 1.5 to 2.5% by weight of polyvinylpyrrolidone and additionally colloidal silicon dioxide. However, these tablets are not textile detergents, but have preferred windshield washer systems for motor vehicles and floor wiping care. When using conventional swelling disintegrants such as starch and cellulose or their derivatives or polymers such as polyvinylpyrrolidone or polyvinyl alcohol in textile detergents, tablets are obtained which disintegrate more or less quickly in water; however, such disintegrants in the sizes required for rapid disintegration lead to problems with residues on the treated laundry.

Accordingly, the object of the invention was to provide a detergent tablet containing effervescent agent which, on the one hand, rapidly disintegrates in the application liquor and on the other hand does not cause any problems with regard to the formation of residues on textiles.

It has now been found that the disintegration problems of a detergent tablet containing an effervescent agent can be avoided by introducing a swellable, water-insoluble disintegration aid into the molded article in addition to the bubbling system.

The object of the invention is therefore, in a first embodiment, a detergent and cleaning agent fora made of compressed particulate detergent and cleaning agent, comprising surfactant (s), builder and, if appropriate, further detergent and cleaning agent components, the shaped body furthermore

a) 1 to 10 wt .-% of one or more swellable, water-insoluble disintegrants and

b) 3 to 60 wt .-% of a gas-developing shower system

contains.

In the context of the present invention, the contents of the agents in a) or b) are briefly referred to below as “component a)” or “component b)”. Here is the term In this context, "component" is to be understood as a pure language construction. In particular, the bubbling system b) can consist of several compounds, which do not necessarily have to be in the form of a single compound. Rather, the total content of the compounds concerned, which is also in completely different individual raw materials or compounds can be present, calculated and referred to as "component b)". Likewise, the swellable, water-insoluble disintegration aids do not necessarily have to be in the form of a single compound. Here too, if necessary, several disintegration aids of the type mentioned can be present in a wide variety of individual raw materials and / or compounds, which are computationally combined to “component a)”

As swellable, water-insoluble disintegration aids {component a)}, use is made above all of polymeric substances with molecular weights between a few tens and hundreds of thousands gmol ^"1. In addition to synthetic polymers such as polyvinylpyrrolidone and polyvinyl alcohol, natural and chemically modified biopolymers are particularly suitable as component a), which can be selected, for example, from the group of alginates, starches and celluloses. Component a) is preferably selected from the natural and synthetic polysaccharides and their derivatives.

These groups include, for example, the pure polysaccharides starch and cellulose, but also the products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses or starches in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as polysaccharide derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses; the group of starch derivatives includes, for example, carboxymethyl starch (CMS).

Of course, microcrystalline cellulose can also be used as a swellable, water-soluble disintegration aid. This cellulose has primary particle sizes of approx. 5 μm and can, for example, be compacted into granules with an average particle size of 200 μm. Such compacts are stable and can be mixed with other substances without disintegrating into the primary particles.

The swellable, water-soluble disintegration aids can not only be used in finely divided powder form, but can also be converted into a coarser granular form by a spray drying, granulating, agglomerating, compacting, pelleting or extrusion process. These "granulated" disintegration aids include not only disintegrants in granular form, but also, for example, those in co-granulated or otherwise compacted form.

Preferred detergent tablets are used as component a) from 1 to 10% by weight, preferably from 2 to 7% by weight and in particular from 3 to 5% by weight, based on the total tablet, of a cellulose or a cellulose derivative. The gas-developing shower system {component b)} can consist of a single substance which releases a gas on contact with water. Among these compounds, the magnesium peroxide mentioned above, which releases oxygen on contact with water, should be mentioned in particular. Usually, however, the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the bubble system used in the detergent tablets according to the invention can be selected on the basis of both economic and ecological aspects. Preferred components b) consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the pure alkali metal carbonates or bicarbonates in question do not have to be be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred for reasons of washing technology.

In preferred detergent tablets, component b) is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 up to 12 and in particular 3 to 10% by weight of an acidifying agent, based in each case on the entire shaped body.

Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group. Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).

In the context of the present invention, preference is given to shaped tablets and detergents in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as acidifying agents in component b).

The detergent tablets of the present invention preferably additionally contain further ingredients customary in detergents from the group of surfactants, builders, bleaches, bleach activators, enzymes, optical brighteners, Foam inhibitors, perfumes and dyes. These substances are described in more detail below.

Anionic, nonionic, cationic and / or amphoteric surfactants can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the molded article is from 5 to 60% by weight, based on the weight of the molded article, with surfactant contents above 15% by weight being preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C ₉ . ₁₃ -Alkylbenzolsul- sulfonates, sulfonates olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfide, obtained, for example, from C; _2. _18- Monoolefιnen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfie products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. Alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C _{] 8} fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C _{] 0} -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. From the washing, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ are - C ₁₅ alkyl sulfates. In addition, 2,3-alkyl sulfates, which are produced for example according to U.S. Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^® are surfactants suitable anion.

The sulfuric acid monoesters of the straight-chain or branched C _7.2 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ . _u -Alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _I2 . ₁₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _g . 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 fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

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

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 is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁₄ - alcohols with 3 EO or 4 EO, C _9.π 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 ranks ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

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

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

R ¹

R-CO-N- [Z] (I) in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 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)

R ^ OR ²

R-CO-N- [Z] (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, with C _M - alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives thereof Rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. The builders that can be contained in the detergent tablets according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

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. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. 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 disilicate Na ₂ Si ₂ O ₅ -yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a module Na ₂ O: SiO ₂ of 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 are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". 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-rays which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be integrated in such a way 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. 20th nm are preferred. Such so-called X-ray 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. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP ^(R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production. If the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₈ fatty alcohols with 2 to 5 Ethylene oxide groups, C _{] 2} -C ₁₄ - fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, 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. This Salts are used because of their builder properties and should not be considered as part of the effervescent system, especially since the salts are not suitable for releasing carbon dioxide from hydrogen carbonates, for example.

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

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated as the sole constituent or as an ingredient of component b). Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular l, 5-diacetyl-2,4-dioxohexahydro-l, 3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetoxy and 2,5-diacetyloxy and 2,5-glycolacetyl, ethylene glycol 2,5-dihydrofuran.

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

Suitable foam inhibitors, which can be part of component b), or used alone as component b), are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ . ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silicic acid or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

In addition, the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight. , each based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof . Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. active ingredients. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

The shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the Moφholino group, have a diethanolamino group , a methyl amino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. 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) diphenyls. Mixtures of the aforementioned brighteners can also be used.

In a further embodiment, the invention relates to a process for the production of the detergent tablets according to the invention by squeezing a particulate detergent and cleaning agent, comprising surfactant (s), builder and, if appropriate, further detergent and detergent components, the detergent and Detergent continues

a) 1 to 10 wt .-% of one or more swellable water-insoluble disintegration aids and b) 3 to 60% by weight of a gas-developing shower system,

each based on the resulting molded article, wherein components a) and b) can both be compounded with other ingredients of the detergent and cleaning agent or can be mixed separately.

The particulate premix to be veφress can be in the form of a pure powder mixture in which components a) and b) are present, but it is preferred that individual raw materials are introduced into the premix in pretreated, in particular precompressed, form. In particular, the disintegration aids are preferably introduced into the premix in the form of granules, pellets, compactates or extrudates. The same also applies to certain other ingredients, such as surfactants, which are introduced into the premix in the form of advantageously builder-containing particles, which can be obtained by spray drying, granulation, pelleting, compacting or extrusion.

In preferred embodiments of the process according to the invention, the particulate detergent and cleaning agent composition is pressed at temperatures below 30 ° C. and pressing forces below 15 N / cm ² . The actual production of the molded article according to the invention is carried out first by dry mixing the components, which may be wholly or partially pre-granulated, and then providing information, in particular compresses to tablets, using conventional methods (for example, as in the conventional patent literature on tablets, especially on the Detergent or cleaning agent area, in particular as described in the above-mentioned patent applications and the article "Tablettierung: Stand der Technik", SÖFW-Journal, 122nd year, pp. 1016-1021 (1996)).

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all usable configurations come into consideration as the spatial shape, for example, the design as a board, the rod or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces and, in particular, linden-shaped configurations with 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 portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points. For the use of laundry detergents in machines of the type customary in Europe with horizontally arranged mechanics, the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from 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 pressed articles.

The spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process. However, it is of course also possible to use the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.

Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, are broken off and into the This principle of the "bar-shaped" shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side. However, it is also possible that the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution. The layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).

In a further preferred embodiment of the invention, a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body, the two outer layers and in the case of the molded body however, the outermost layers are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body. Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like. Similar effects can also be achieved by coating individual constituents of the detergent and cleaning agent composition to be treated or the entire molded body. For this purpose, the bodies to be coated can be sprayed with aqueous solutions or emulsions, for example, or by the process of melting. get a coating.

The moldings according to the invention, in particular the detergent molds and bleach moldings which have been poorly disintegrating and poorly soluble up to now, have excellent disintegration properties due to the content of water-insoluble, swellable disintegration aid and effervescent system {components a) and b)}. This can be tested, for example, under critical conditions in a conventional household washing machine (use directly in the washing liquor using a conventional dosing device, delicate washing program or colored laundry, washing temperature at most 40 ° C).

In a further embodiment of the invention, a washing method is therefore claimed, the molded body being introduced into the washing liquor via the induction device of the household washing machine. The dissolving times of the molded articles in the washing machine are preferably less than 8 minutes and in particular less than 5 minutes. A further embodiment of the invention claims a washing method in which the molded body - optionally with a metering aid - is placed directly on the laundry which is located in the drum of a household washing machine. Here, the molded body can advantageously be added directly to the laundry, ie without additional metering aid; the use of known dosing aids such as bags, sachets, plastic containers or the like is also possible without any problems. Examples

By washing a particulate detergent and cleaning agent composition, the detergent tablets 1 and 2 according to the invention and comparative examples 3 and 4 were produced, which had a composition according to Table 1.

The comparative examples contained either no component a) (example 3) or no component b) (example 4), small amounts of Na ₂ CO _{3 being used} as builders.

Table 1: Detergent and molded article [wt .-%]:

*) mixed separately

The hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.

To determine the tablet disintegration, the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely.

For the wash-in test, 3 tablets of 40 g each were placed in the wash-in chamber of the washing machine in question. After the induction process, the residue is dried in the chamber and weighed out.

The experimental data are shown in Table 2: Table 2: Detergent tablets [physical data]

Claims

Patent claims

1. Detergent and cleaning agent foraiköφer made of compressed particulate detergent and cleaning agent, comprising surfactant (s), builder and optionally further detergent and cleaning agent components, characterized in that the molded article continues

a) 1 to 10 wt .-% of one or more swellable, water-insoluble disintegrants and

b) 3 to 60 wt .-% of a gas-developing shower system

contains.

2. Detergent and body form according to claim 1, characterized in that component a) is selected from the natural and synthetic polysaccharides and their derivatives.

3. Detergent form according to one of claims 1 or 2, characterized in that component b) consists of alkali metal carbonate and / or - hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.

4. Detergent and molded article according to one of claims 1 to 3, characterized in that as component a) 1 to 10 wt .-%, preferably 2 to 7 wt .-% and in particular 3 to 5 wt .-%, based on the entire molded body, a cellulose or a cellulose derivative can be used.

5. Detergent and molded article according to one of claims 1 to 4, characterized in that as component b) 2 to 20 wt .-%, preferably 3 to 15 % By weight and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of an acidifying agent, in each case based on the total molded body, are used.

6. Detergent form according to one of claims 3 to 5, characterized in that a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures of these are used as acidifying agents in component b).

7. Process for the production of detergent tablets by pressing a particulate detergent and detergent, comprising surfactant (s), builder and optionally further detergent and cleaning agent components, characterized in that the detergent and cleaning agent to be veφress continue

a) 1 to 10 wt .-% of one or more swellable, water-insoluble disintegrants and

b) 3 to 60% by weight of a gas-developing shower system,

each based on the resulting molded body, wherein components a) and b) can both be compounded with other ingredients of the detergent and cleaning agent or can be mixed separately.

8. The method according to claim 7, characterized in that the particulate detergent and cleaning composition is veφreßt at temperatures below 30 ° C and pressing forces below 15 N / cm ² .

9. Washing method using a molded article according to one of claims 1 to 6, characterized in that the molded article is introduced into the washing liquor via the induction device of a household washing machine.

10. Washing method using a molded body according to one of claims 1 to 6, characterized in that the molded body is introduced directly with the laundry into the drum of a household washing machine.