WO2000044871A1 - Abrasion-resistant moulded detergent and cleaning agent articles with a high non-ionic surface-active agent content - Google Patents

Abstract

The invention relates to moulded detergent and cleaning agent articles which are characterized by high hardness and good detergent injection properties as well as high abrasion resistance. Such moulded articles can be obtained if the ratio of non-ionic to anionic surface-active agents contained in the moulded articles is between 0.4:1 and 3:1.

Description

 "Abrasion-resistant detergent tablets with high non-ionic surfactant content '

The present invention is in the field of compact moldings which have washing and cleaning properties. Such detergent tablets comprise, for example, detergent tablets for washing textiles, detergent tablets for machine dishwashing or cleaning hard surfaces, bleach tablets for use in washing machines or dishwashers, water softening tablets or stain remover tablets. In particular, the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.

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 detergents: they are easier to dose and handle and, thanks to their compact structure, have advantages for storage and transportation. 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 of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process. The delayed disintegration of the moldings has the further disadvantage that conventional detergent tablets cannot be washed in via the induction chamber of household washing machines, since the tablets do not disintegrate into secondary particles that are small enough to pass from the induction chamber into the washing drum to be washed in. Another problem that arises in particular with detergent tablets is the friability of the tablets or their often insufficient stability against abrasion. Sufficiently break-resistant, ie hard, detergent tablets can be produced, but these are often not able to withstand the stresses during packaging, transport and handling, ie falling and rubbing loads, so that edge breaking and abrasion phenomena impair the appearance of the tablet or even lead to a complete destruction of the molded body structure.

Solutions to the problem of the friability or abrasion stability of detergent tablets are only disclosed in the prior art in the older German patent application DE 198 41 146.4 (Henkel KGaA). The solution disclosed herein consists in the incorporation of liquid, non-surfactant binders into the premixes to be pressed.

The use of surfactants in detergent tablets has been the subject of numerous publications. Formulations rich in nonionic surfactants are described in particular in the following publications.

European patent application EP 355 626 (Henkel KGaA) discloses a method for producing detergent tablets which are free or low in phosphate, in which at least two powdery to granular components (A) and (B) are produced, which are mixed and tabletted. Component (A) contains the total amount of anionic surfactants, component (B) 75 to 100% of the total amount of nonionic surfactants.

European patent application EP 466 485 (Unilever) also describes detergent tablets which contain builders and anionic and nonionic surfactants. The premix to be pressed consists here of particles which consist of 20 to 100% anionic surfactant and preferably of anionic surfactant-free particles which may contain nonionic surfactant. This document does not disclose a ratio to be maintained between nonionic and anionic surfactants. The problem of insufficient abrasion stability is also not mentioned. Detergent tablets, which in addition to high amounts of nonionic surfactant necessarily contain potassium carbonate, are described in European patent application EP 482 627 (Kao Corp.). According to the teaching of this document, the solubility of the tablets is improved by a special weight ratio between nonionic surfactant and potassium carbonate. In this document, too, anion / nonionic surfactant ratios are not disclosed, nor is the problem of abrasion stability dealt with.

The use of ethoxylated alcohols whose average C chain length is less than 12 because at least 25% of the alkyl chains have a length of less than 12 carbon atoms is disclosed in EP 598 586 (Unilever). This publication does not explicitly describe detergent tablets which also contain anionic surfactant in addition to the nonionic surfactant. A ratio to be observed between nio- and anionic surfactants is just as little disclosed as the problem of abrasion.

The present invention was based on the object of providing moldings which, given a given hardness, are distinguished by short disintegration times and can therefore also be metered via the dispensing chamber of household washing machines. In addition to these requirements, the moldings should have increased stability against falling and rubbing loads, i.e. an improved, i.e. have reduced friability and reduced abrasion behavior. If possible, the advantageous properties should be achieved by the preparation of detergent and cleaning agent ingredients in order to be able to dispense with the addition of "non-recipe" auxiliaries that do not perform any washing and cleaning work. From this point of view, the active substances were suitable especially the washing-active substances.

It has now been found that the weight ratio between nonionic and anionic surfactants in the overall formulation has a decisive influence on friability.

The present invention relates to detergent tablets made from compressed, particulate detergent and detergent containing builders, Anionic and nonionic surfactants and optionally further ingredients of washing and cleaning agents, in which the ratio of nonionic to anionic surfactants is in the range from 0.4: 1 to 3: 1.

In the context of the present invention, the term “ratio” denotes the quotient of the percentages by weight of nonionic and anionic surfactants, the percentages by weight referring to the entire molded article. It is not relevant here whether anionic and nonionic surfactants have been incorporated into the detergent tablets in different ways or whether they are present in different phases or regions of the tablet In preferred embodiments, the ratio is in an even narrower range, so that detergent tablets are preferred which the ratio of nonionic to anionic surfactants is in the range from 0.45: 1 to 2.5: 1, preferably from 0.5: 1 to 2: 1 and in particular from 0.75: 1 to 1.5: 1 .

The detergent tablets according to the invention contain builders as well as anionic and nonionic surfactants as mandatory components. These are described below.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C _-13 - alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C ₁₂ ι ₈ -Monoolefmen with terminal or internal double bond by sulfonation with Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates, which are for example obtained from _2- Cι ι ₈ alkanes by sulfochlorination or sulfoxidation and 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 glycerin esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation 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.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁ -C ₀ 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 ₂ -C ₁₆ alkyl sulfates and C ₁₂ - C ₁₅ alkyl sulfates and C ₄ -Ci ₅ alkyl sulfates are preferred for washing technology reasons. 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 DAIST, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-2 ι alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C ₉ π alcohols with an average of 3.5 moles of ethylene oxide (EO) or Cι _2- ι ₈ fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred Sul- fosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which are non-ionic surfactants in themselves (see description 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 from natural fatty acids, e.g. Coconut, 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 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.

In the context of the present invention, detergent tablets are preferred in which the anionic surfactant content in the tablet is above 5% by weight, preferably above 7.5% by weight and in particular above 10% by weight based on the weight of the molded body.

When selecting the anionic surfactants, there are no basic conditions to be observed that prevent freedom of formulation. However, preferred surfactant granules have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent tablets. The preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, 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 detergent tablets 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 has a methyl or linear branching in the 2-position may be 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 fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. Preferred ethoxylated alcohols include, for example, _2- Cι ι ₄ alcohols containing 3 EO or 4 EO, C _{9 n-alcohol} with 7 EO, C13-1 ₅ - alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C _{12 18} - alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Cπ-π alcohol containing 3 EO and Cι ₂ -i ₈ alcohol containing 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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 esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Usable alkyl polyglycosides satisfy the general formula RO (G) _z , in which R is a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Symbol is that for a glyco 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 radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

The surfactant granules can preferably contain alkyl polyglycosides, with APG contents of more than 0.2% by weight, based on the entire molded body, being preferred. Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.

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 represents an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, 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 propoxylated derivatives of this residue.

[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.

In the context of the present invention, detergent tablets are preferred in which the content of nonionic surfactants in the tablet is above 2% by weight, preferably above 5% by weight and in particular above 7.5% by weight based on the molded body weight.

In the context of the present invention, nonionic surfactants from all of the above-mentioned groups can be used. Regardless of the chemical nature of the nonionic surfactants used, it is preferred that the nonionic surfactants contained in the detergent tablets have a melting point below of 40 ° C, preferably below 30 ° C and in particular below 20 ° C.

As already mentioned above, the nonionic and anionic surfactants can be incorporated into the detergent tablets according to the invention in a wide variety of ways. They can be added to the premix to be treated, for example in solid form, or sprayed out of the premix in liquid form. It has proven to be advantageous to produce surfactant granules which are mixed with other powdery components to form the premix to be tabletted and pressed. According to the invention, detergent tablets are preferred which contain the surfactants in the form of a surfactant-containing granulate in amounts of from 40 to 95% by weight, preferably from 45 to 85% by weight and in particular from 55 to 75% by weight. -%, each based on the molded body weight, is contained in the shaped bodies.

In order to incorporate the desired amount of detergent substance into the detergent tablets, detergent tablets are preferred in which the surfactant granules contain from 5 to 60% by weight, preferably from 10 to 50% by weight and in particular from 15 up to 40 wt .-%, each based on the weight of the surfactant granules. In particular, detergent tablets in which the anionic surfactant content of the surfactant granules is 5 to 45% by weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight, in each case based on the weight of the surfactant granules and detergent tablets, in which the content of the surfactant granules of nonionic surfactants is 1 to 30% by weight, preferably 5 to 25% by weight and in particular 7.5 to 20% by weight, in each case based on the weight of the surfactant granules , is preferred according to the invention.

In order to obtain storage-stable and free-flowing surfactant granules, it is preferred if carrier substances are added in the preparation of the surfactant granules, ie the surfactant granules contain builders. Other ingredients of detergents and cleaning agents, especially so-called small components such as optical brighteners, poly- Mers, defoamers, phosphonates, dyes and fragrances can be part of the surfactant granules. These substances are described below.

In addition to the wash-active substances, builders are the most important ingredients in detergents and cleaning agents. The washing and cleaning agent shaped bodies according to the invention can contain all of the builders normally used in washing and cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.

It has been shown that the effect of improving the abrasion stability is stronger if the surfactant granules contain only small amounts of carbonates. In preferred washing and cleaning agent shaped bodies, the potassium carbonate content of the shaped body is below 10% by weight, preferably below 7.5% by weight and in particular below 5% by weight, in each case based on the molded body weight, with potassium carbonate-free molded bodies being particularly preferred are preferred.

Crystalline, layered sodium silicates suitable as builders have the general formula NaMSi _x O _x + ι ^' HO, 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 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 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which delay the dissolution, can also be used are and have secondary washing properties. The dissolving delay compared to conventional amorphous sodium silicates can be done in various ways, for example by surface treatment, compounding, compacting / compression or caused 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. 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. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

If desired, in addition to the amount of zeolite of the P and / or X type that is usually introduced by the surfactant granules, further zeolite can be incorporated into the premix by adding zeolite as a treatment component. The finely crystalline, synthetic and bound water-containing zeolite used is preferably a type A, P, X or Y zeolite. However, zeolite X and mixtures of A, X and / or P are also suitable. 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.

Preferred detergent tablets contain, based on the tablet weight, less than 5% by weight, preferably less than 2% by weight and in particular less than 1% by weight of silica (s). Organic cobuilders which can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), 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.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the Molecular weight information from which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.

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

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

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

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers . Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 owns. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0427 349, EP-A-0 472 042 and EP-A-0 542 496 and the international national patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.

Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or ammoalkane phosphonates. Among the hydroxyalkane phosphonates, l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred ammoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.

The production of surfactant-containing granules is widely described in the prior art, and in addition to extensive patent literature, numerous review articles and monographs can also be used. W.Hermann de Groot, I. Adami, G.F. Moretti "The Manufacture of Modern Detergent Powders", Hermann de Groot Academic Publisher, Wassenaar, 1995 various spray drying, mixing and granulating processes for the production of detergents and cleaning agents.

For energetic reasons, it is preferred in the context of the present invention if the granules containing surfactant are not produced by spray drying, but rather by means of a granulation process. In addition to the conventional granulation and agglomeration processes, which can be carried out in a wide variety of mixing granulators and mixing agglomerators, press agglomeration processes can also be used, for example. Methods in which the surfactant-containing granules are produced by granulation, agglomeration, press agglomeration or a combination of these methods are therefore preferred.

The granulation can be carried out in a large number of apparatuses customarily used in the detergent and cleaning agent industry. For example, it is possible to use the rounding agents commonly used in pharmacy. In such turntable devices, the residence time of the granules is usually less than 20 seconds. Conventional mixers and mixing granulators are also suitable for granulation. Both high-intensity mixers ("high-shear mixers") and normal mixers with lower circulation speeds can be used as mixers. Suitable mixers are, for example Eirich ^® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ^® Flexomix, the Fukae ^® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co., Japan), the Lödige ^® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais ^® series T or KT (trademark of Drais- Werke GmbH, Mannheim). The residence times of the granules in the mixers are in the range of less than 60 seconds, the Dwell time also depends on the speed of rotation of the mixer. The dwell times are reduced accordingly the faster the mixer runs. The residence times of the granules in the mixer / rounder are preferably less than one minute, preferably less than 15 seconds. Dwell times of up to 20 minutes are set in slow-running mixers, for example a Lödige KM, dwell times below 10 minutes being preferred because of the process economy.

In the process of press agglomeration, the surfactant-containing granules are compressed under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner. The technically most important press agglomeration processes are extrusion, roller compaction, pelleting and tableting. In the context of the present invention, preferred press agglomeration processes used to produce the surfactant-containing granules are extrusion, roller compaction and pelletization.

In a preferred embodiment of the invention, the surfactant-containing granulate is preferably fed continuously to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder granulating head of which can be heated to the predetermined extrusion temperature . Under the shear action of the extruder screws, the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this embodiment, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.8 to 5 mm and in particular in the range from approximately 1.0 to 3 mm. The country In an important embodiment, the ge / diameter ratio of the chipped primary granules is in the range from about 1: 1 to about 3: 1. Furthermore, it is preferred to feed the still plastic primary granulate to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained. Alternatively, extrusions / readings can also be carried out in low-pressure extruders, in the Kahl press or in the extruder.

In a further preferred embodiment of the present invention, the production process for the surfactant-containing granules is carried out by means of roller compaction. Here, the granules containing surfactant are metered in between two smooth rollers or with depressions of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rollers, smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs or individual pellets can be produced, in which, for example, certain shapes of the later granules or shaped bodies can be specified. The sliver belt is subsequently broken up into smaller pieces by a knocking-off and crushing process and can be processed into granules in this way, which can be further tempered, in particular in an approximately spherical shape, by further known surface treatment processes.

In a further preferred embodiment of the present invention, the preparation of the surfactant-containing granules is carried out by means of pelleting. Here, the granules containing surfactant are applied to a perforated surface and pressed through the holes by means of a pressure-producing body. In conventional embodiments of pellet presses, the surfactant-containing granules are compressed under pressure, plasticized, pressed through a perforated surface in the form of fine strands by means of a rotating roller and finally comminuted to granules with a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. So flat perforated plates are used, for example, as are concave or convex ring matrices through which the material is pressed by means of one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation. An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH). The ring die press disclosed in this document consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizer to set a desired temperature of the premix.

The surfactant granules or the surfactant granules are / are then mixed with further preparation components to form a premix, which can then be pressed into detergent tablets. In addition to the ingredients already mentioned, the premix to be treated can contain other ingredients that are customary in washing and cleaning agents, in particular from the group of builders, disintegration aids, bleaching agents, bleach activators, enzymes, pH-adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors , Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors. However, all or part of the substances mentioned can already be part of the surfactant granules.

The present invention therefore also relates to a process for the production of detergent tablets by mixing surfactant-containing granules with finely divided preparation components and subsequent molding in a manner known per se, the ratio of nonionic to anionic surfactants in the tablets being in the range from 0.4 : 1 to 3: 1. A variant is also preferred in the process according to the invention in which the ratio of nonionic to anionic surfactants in the shaped bodies is in the range from 0.45: 1 to 2.5: 1, preferably from 0.5: 1 to 2: 1 and in particular from 0.75: 1 to 1.5: 1.

As mentioned above, the surfactants can be introduced into the moldings in different ways, the incorporation via surfactant granules being particularly advantageous. Here, process engineering advantages can result from a separation of anionic and nonionic surfactants, so that processes in which two surfactant-containing granules are mixed with finely divided processing components and subsequently molded in a manner known per se, the one surfactant granulate comprising the anionic surfactants and the other surfactant granulate contains nonionic surfactants, are preferred according to the invention.

Of course, it is also possible according to the invention to use only a single surfactant granulate, that is to say to carry out a process variant in which a surfactant-containing granulate is mixed with finely divided preparation components and subsequently molded in a manner known per se, the surfactant granulate containing both anionic and nonionic surfactants.

If this process variant is chosen, it is preferred that the surfactant-containing granules have a total surfactant content of 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, based in each case on the Weight of the surfactant granules, the anionic surfactant content of the surfactant granules preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight and in particular 15 to 35% by weight, and the nonionic surfactant content of the surfactant granules preferably 1 to 30% by weight, particularly preferably 5 to 25% by weight and in particular 7.5 to 20% by weight, in each case based on the weight of the surfactant granules.

In addition to the surfactant granules (or the surfactant granules), the detergent tablets of the present invention may contain further detergent ingredients, for example disintegration aids, bleaches, Bleach activators, dyes and fragrances etc. These substances, which can also be a component of the surfactant granules, are described below.

In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, 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, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.

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

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

The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated. Detergent tablets, which contain disintegrants in granular or optionally granulated form, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention. Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, to granules with an average particle size of 200 μm.

To further improve the mechanical property, such as abrasion resistance, it is also possible to coat the molded body with a coating that covers the entire molded body. Coated detergent tablets of this type can be produced by spraying a melt or solution of the coating material onto the molded article or by immersing the molded article in the melt or solution. In preferred embodiments of the present invention, however, the detergent tablets are not coated with a coating that covers the entire tablet.

Among the compounds which serve as bleaching agents and supply HO ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that 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, regardless of which other ingredients are contained in the molded articles. 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 bleaching agents are the diacyl peroxides, such as 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 monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidopercapid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid diperoxyacid, diperoxyacid, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine-releasing substances can also be used as bleaching agents in molded articles for automatic dishwashing. Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,

Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C. and below, bleach activators can be incorporated into the molded body. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the 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, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially special n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called 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. 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 also be used as bleaching catalysts.

Enzymes in particular include those from the classes of hydrolases such as proteases, esterases, lipases or enzymes having a hypolytic action, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures are, for example, from protease and amylase or protease and lipase or enzymes having a hypolytic action or protease and cellulase or from cellulase and lipase or enzymes having a hpolytic effect or from protease, amylase and lipase or enzymes having a hypolytic action or protease, lipase or Enzymes and cellulase having a hypolytic effect, but in particular protease and / or lipase-containing mixtures or mixtures with enzymes having a hypolytic effect are of particular interest. Known cutinases are examples of such hypolytic enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular alpha- Amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases. The enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.

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, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or 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.

The shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-moφholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the Moφholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) - diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyls. Mixtures of the aforementioned brighteners can also be used.

Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and sensorially "typical and distinctive" product in addition to performance. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propalate and benzylate propionate. The ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, cc-Isomethylionon and Methyl-cedrylketon, to the alcohols Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol and Terpinerol, to the hydrocarbons belong mainly the Teφene like Limonen and Pinen. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. 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 dye content of the detergent tablets according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.

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

In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them.

Before the particulate premix is pressed into detergent tablets, the premix can be "powdered" with finely divided surface treatment agents. This can be of advantage for the quality and physical properties of both the premix (storage, molding) as well as the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (compare Donald W. Breck: “Zeolite Molecular Sieves”, John Wiley & Sons, New York , London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X, zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred.

In the context of the present invention, processes for the production of detergent tablets are preferred, in which the or one of the subsequently mixed fine-particle treatment components is a faujasite-type zeolite with particle sizes below 100 μm, preferably below 100 μm and in particular below 5 μm and at least 0.1 2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be treated. In preferred processes according to the invention, the premix to be veφre has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1, and further contains one or more substances from the group of disintegration aids, bleaching agents, Bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.

To produce the shaped bodies according to the invention, the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to below as tableting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool. The constant metering, even at high mold throughputs, is preferably achieved via a volumetric metering system of the premix. In the further course of the tabletting process, the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed. Depending on the physical properties of the premix, some of the premix particles are also crushed and sintering of the premix occurs at even higher pressures. With increasing pressing speed, that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities. In the last step of tableting, the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point, it's just that Weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).

Tableting is carried out in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper punch used to build up the drain, the lower punch also moves towards the upper punch during the pressing process, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine. The pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disc, the number of die bores being increased accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table. 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 punch, whereby the press-back can in turn be built up only by the upper or lower punch, but also by both stamps. The die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation. Wherever a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks. The die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The press pack on the premix is individual via the press paths for the upper and lower punches adjustable, whereby the build-up of the pressure happens by rolling the punch shaft heads past adjustable pressure rollers.

Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet. For the production of two-layer and multi-layer molded bodies, several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling. By means of suitable process control, jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible. Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million molded articles per hour.

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

The molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar 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 portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. However, it is also possible to form compacts which combine a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by 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 panel-like structure with alternately 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 Machine can be entered. This principle of the "bar-shaped" shaped body detergent can also be realized 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 both for example, components are contained in the moldings that mutually influence each other negatively, so 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 if 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, i.e. 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 shell-shaped molded body the outermost layers, however, 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 article. For this purpose, the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method. After pressing, the detergent tablets have a high stability. The breaking strength of cylindrical shaped bodies can be determined via the measured quantity of the diametrical break load. This can be determined according to

2P σ = πDt

Herein σ stands for diametrical fracture stress (DFS) in Pa, P is the force in N, which leads to the pressure exerted on the molded body, which causes the molded body to break, D is the molded body diameter in meters and t the height of the molded body.

Another object of the present invention is the use of surfactant-containing granules which, after being mixed with finely divided processing components, are pressed in a manner known per se to form detergent and cleaning compositions and in which the ratio of nonionic to anionic surfactants is in the range from 0.4: 1 to 3: 1, is to improve the abrasion resistance of detergent tablets. By using the surfactants in a defined weight ratio, the physical properties of the molded body can be improved, as the following examples show:

Examples:

Various surfactant granules were produced by wet granulation in a 130 liter ploughshare mixer from Lödige, the contents of which varied in nonionic and anionic surfactants. Following the granulation, the granules were dried in an aerodynamic fluidized bed apparatus at an inlet air temperature of 60 ° C. for 30 minutes. After drying, the granules were sieved to remove the fine particles <0.6 mm and coarse particles> 1.6 mm.

The surfactant granules E1 to E4 or VI and V2 were then processed with further components to form a compressible premix, after which the pressing into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) was carried out in a Korsch eccentric press . The measured values of the tablet hardness and disintegration times are in each case the mean values of a double determination, the individual values per molded body type varying by a maximum of 2 N or 2 s. The composition of the surfactant granules is shown in Table 1, the composition of the premixes to be treated (and thus the molded article) is shown in Table 2.

Table 1: Composition of the surfactant granules [% by weight]

Table 2: Composition of the premixes [% by weight]:

* Terephthalic acid-ethylene glycol-polyethylene glycol ester (Rhodia, Rhône-Poulenc)

After two days of storage, the hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force which the tablet withstood being determined.

The washability was tested in a Miele Novotronic W918 washing machine (main wash program, 60 ° C). After washing in with three tablets and cold city water (16 ° dH), the residues were dried and weighed out.

The abrasion stability was determined by placing a tablet on a sieve with a mesh size of 1.6 mm. This sieve was then placed in a Retsch analytical sieve machine and with an amplitude of 2 mm over 120 seconds claimed. By weighing the tablet lying on the sieve before and after the stress, the abrasion can be calculated in%. The experimental data are shown in Table 3:

Table 3: Detergent tablets [physical data]

While the tablet hardness and residue values of the molded bodies E and V are in the same range, the molded bodies E according to the invention show a significantly better stability against the frictional load caused by the vibrating screen. A nonionic surfactant / anionic surfactant ratio below 0.4: 1 (VI, V2) leads to moldings which lose a quarter (VI) or 2/5 (V2) of their mass. With such drastic mass losses, the original shape of the molded body is no longer visible. The application properties are consequently further improved by the ratio according to the invention between nonionic and anionic surfactants.

Claims

Claims: 1. washing and cleaning agent shaped body made of compressed, particulate washing and cleaning agent, containing builders, anionic and nonionic surfactants and optionally further ingredients of washing and cleaning agents, characterized in that the ratio of nonionic to anionic surfactants in the range of 0.4: 1 to 3: 1. 2. Detergent form according to claim 1, characterized in that the ratio of nonionic to anionic surfactants in the range from 0.45: 1 to 2.5: 1, preferably from 0.5: 1 to 2: 1 and in particular from 0.75: 1 to 1.5: 1. 3. Detergent and molded article according to one of claims 1 or 2, characterized in that the anionic surfactant content of the molded article is above 5% by weight, preferably above 7.5% by weight and in particular above 10% by weight. -%, based in each case on the molded body weight. 4. Detergent and molded article according to one of claims 1 to 3, characterized in that the content of the molded article of nonionic surfactants is above 2% by weight, preferably above 5% by weight and in particular above 7.5% by weight. -%, based in each case on the molded body weight. 5. Detergent form according to one of claims 1 to 4, characterized in that they contain the surfactants in the form of a surfactant-containing granules in amounts of 40 to 95 wt .-%, preferably from 45 to 85 wt .-% and in particular from 55 to 75% by weight, based in each case on the molded body weight, is contained in the molded bodies. 6. Detergent form according to claim 5, characterized in that the surfactant granules have a surfactant content of 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, based in each case on the Weight of the surfactant granules. 7. Detergent and molded article according to one of claims 5 or 6, characterized in that the anionic surfactant content of the surfactant granules is 5 to 45% by weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight. , each based on the weight of the surfactant granules. 8. Detergent form according to one of claims 5 to 7, characterized in that the content of the surfactant granules of nonionic surfactants 1 to 30 wt .-%, preferably 5 to 25 wt .-% and in particular 7.5 to 20 wt. -%, each based on the weight of the surfactant granules. 9. Detergent and molded article according to one of claims 1 to 8, characterized in that the potassium carbonate content of the molded article is below 10% by weight, preferably below 7.5% by weight and in particular below 5% by weight, in each case based on the molded body weight, with potassium carbonate-free molded bodies being particularly preferred. 10. Detergent and molded article according to one of claims 1 to 9, characterized in that the nonionic surfactants contained in it have a melting point below 40 ° C, preferably below 30 ° C and in particular below 20 ° C. 11. Process for the production of detergent tablets by mixing surfactant-containing granules with finely divided preparation components and subsequent molding in a manner known per se, characterized in that the ratio of nonionic to anionic surfactants in the tablets in the range from 0.4: 1 to 3: 1. 12. The method according to claim 11, characterized in that the ratio of nonionic to anionic surfactants in the shaped bodies in the range from 0.45: 1 to 2.5: 1, preferably from 0.5: 1 to 2: 1 and in particular from 0.75: 1 to 1.5: 1. 13. The method according to any one of claims 11 or 12, characterized in that two surfactant-containing granules are mixed with finely divided processing components and subsequently molded in a conventional manner, the one surfactant granules containing the anionic surfactants and the other surfactant granules containing the nonionic surfactants. 14. The method according to any one of claims 11 or 12, characterized in that a surfactant-containing granules are mixed with finely divided processing components and subsequently molded in a conventional manner, the surfactant granules containing both anionic and nonionic surfactants. 15. The method according spoke 14, characterized in that the surfactant-containing granules total surfactant contents of 5 to 60 wt .-%, preferably from 10 to 50 wt .-% and in particular from 15 to 40 wt .-%, each based on the Weight of the surfactant granules, the anionic surfactant content of the surfactant granules preferably 5 to 45% by weight, particularly preferably 10 to 40% by weight and in particular 15 to 35% by weight, and the nonionic surfactant content of the surfactant granules preferably 1 to 30% by weight, particularly preferably 5 to 25% by weight and in particular 7.5 to 20% by weight, in each case based on the weight of the surfactant granules. 16. The method according to any one of claims 11 to 15, characterized in that the surfactant-containing granulate (s) is / are produced by granulation, agglomeration, press agglomeration or a combination of these processes. 17. The method according to any one of claims 11 to 16, characterized in that the premix to be veφressende a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1. 18. The method according to any one of claims 11 to 17, characterized in that the premix to be veφressing further one or more substances from the group of disintegration aids, bleaching agents, bleach activators, enzymes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, Silicone oils, Contains anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors. 19. Use of surfactant-containing granules which, after being mixed with finely divided preparation components, are pressed in a manner known per se to form detergent tablets and in which the ratio of nonionic to anionic surfactants is in the range from 0.4: 1 to 3: 1, lies, to improve the abrasion stability of detergent tablets.