SK163199A3 - Detergent shaped body with enhanced dissolving properties - Google Patents

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

The present invention relates to the field of compact shaped articles having washing and cleaning properties. In particular, the invention relates to detergent molded articles such as detergent tablets, dishwasher tablets, stain removal tablets or water softening tablets for domestic use, in particular for machine use.

BACKGROUND OF THE INVENTION

Molded detergent products are described extensively in the prior art and are enjoyed by users for easy dosing of increasing popularity. Tablet detergents and detergents have a number of advantages over powder powders: they are easier to dispense and handle, and because of their compact structure they have advantages in storage and transport. In the patent literature, the shaped articles of detergents and cleaning agents are subsequently described in detail. A problem often encountered in the use of detergent molded articles is too low the rate of disintegration and dissolution of the molded article under the conditions of use. Because sufficiently stable, i.e., molded and fracture resistant articles can only be produced by

Even at comparatively high pressures, there is a strong compaction of the components of the molded article and thus a delayed disintegration of the molded article in the water bath and thus a slow release of the active ingredients in the washing or cleaning process.

The problem of long disintegration times of highly compressed molded articles is known in particular from pharmacy, where certain disintegrating aids, so-called tablet disintegrants, have long been used to shorten disintegration times. Tablet disintegrants or disintegrants are understood to mean:

-2Proppa (9th edition, Vol. 6, page 4440) and Voigt "Lehrbuch der pharmazeutischen Technologie" (6th edition, 1987, pages 182 to 184) excipients that promote rapid disintegration of tablets in water or gastric juice and release of the drug in the resorbable form.

"Hagers Handbuch der pharmazeutischen Praxis" (5th edition, 1991, page 942) divides disintegrants or disintegrants according to their mechanism of action into different classes of compounds, the most important disintegration mechanisms being the swelling mechanism, the deformation mechanism ), a wicking mechanism, a repulsion mechanism, as well as the development of gas bubbles in contact with water (effervescent tablets). In the swelling mechanism, the particles swell through the penetrating water and increase their volume. This causes local stresses that spread throughout the tablet, leading to the breakdown of the compressed structure. The deformation mechanism differs from the swelling mechanism in that the swellable particles are compacted prior to compression during tabletting and now reach their original size upon contact with water. In the wick mechanism, water is sucked in by the disintegrant inside the shaped article and thus releases the bonding forces between the particles, which also leads to the disintegration of the shaped article. The repulsion mechanism additionally differs from these in that the particles released by the water absorbed into the pores repel each other by the generated electrical forces. A fundamentally different mechanism is the basis of 'effervescent tablets containing active substances or active substance systems which, in contact with water, emit gaseous substances which crack the shaped article. In addition, it is also known to use hydrophilizing agents which provide for better wetting of the compressed particles with water and thus faster disintegration.

While it is possible to easily delimit the substances acting under the latter two mechanisms from the other disintegration mechanisms, it is not always possible to unequivocally separate the effects based on the swelling and deformation mechanism as well as the wick and repulsion mechanisms, and therefore for practical reasons, a more effective division into hydrophilizing agents, gas release systems and swellable disintegrants.

The use of different disintegrants alone or in combination with each other is known from pharmaceutical applications. Thus, EP-B-0 396 335 (Beecham Group PLC) discloses chewable tablets which contain, in addition to 1 to 30 wt. from 0.5 to 20 wt. % citric, tartaric, adipic, fumaric or maleic acid and 0.5 to 30 wt. % of sodium, potassium or calcium bicarbonate or sodium glycine carbonate additionally 5 to 30 wt. a disintegrant such as (modified) cellulose, polyvinylpyrrolidone or starch glycolate. The advantage of these chewable tablets is, according to the data in the description, a pleasant application and a pleasant feeling during reception.

Combinations of effervescent granules and swelling disintegrants are known from JP 06 024 959 (BAYER YAKUHIN KK, Derwent Abstract). It discloses pharmaceutical compounds in the form of tablets wherein the active ingredients are mixed with a disintegrant (methylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone) and partially coated with disintegrants which contain a swellable gel-forming polymer (sodium alginate, carrageenan, as a polyethylene oxide generating system ₎ . These tablets are praised despite the use of a pair of disintegrant systems as a sustained release drug carrier.

The proposed solutions lead to the desired success in the manufacture of pharmaceutical tablets.

In the field of detergents, they contribute to improving the disintegration properties of active detergent tablets; however, the improvement achieved is not sufficient in many cases. This is particularly true when the proportion of sticky organic substances in the tablet, such as anionic and / or nonionic surfactants, increases. Additionally, the use of disintegrants in shaped articles may be used | ¹ 'of detergent and cleaning product products lead to specific problems which are completely unknown to the pharmaceuticals.

Thus, for example, the use of an effervescent system in detergent tablets does not cause the desired rapid disintegration, much more potent at the beginning is the effervescence and disintegration known from conventional effervescent tablets, but stagnates after a short time, and the tablet does not further disintegrate. Apparently, the detergent and cleaning aids mentioned above form a water-impermeable layer after a short time, which prevents water from penetrating into the tablet and thereby disintegrating it.

Subsequently, for example, European Patent Application EP-A-0 466 484 (Unilever) describes tablets of compressed detergent particles which contain, in addition to surfactants and activating additives, other detergent ingredients, with swellable agents being preferred for binder / disintegrant content .

Effervescent detergent tablets are described in DE 35 35 516 (Bucher). These tablets contain 2 to 6 wt. % surfactant, 40 to 60 wt. % bicarbonate, 33 to 53 wt. % solid organic acid (especially 2: 3 - a mixture of citric acid and tartaric acid), 1.5 to 2.5 wt. polyvinylpyrrolidone as well as additionally colloidal silica. However, these tablets are not a fabric washing agent but are advantageous for use in vehicle windshield washers or as a floor washing agent.

Using conventional swellable disintegrants such as starches and cellulose, or derivatives or polymers thereof such as polyvinylpyrrolidone or polyvinyl alcohol in fabric washing compositions, tablets that disintegrate more or less rapidly in water are obtained; however, such disintegrants lead to problems with residues on the laundry to be treated at the amounts required for rapid disintegration.

Accordingly, the object of the invention was to provide molded detergent articles containing effervescent agents which, on the one hand, rapidly disintegrate in the application bath and, on the other hand, do not cause any problems with respect to the formation of residues on fabrics.

It has been found that the disintegration problem of the detergent-containing detergent article containing the effervescent compositions can be avoided by additionally adding a swellable, water-insoluble disintegrating aid to the effervescent system in the shaped article.

SUMMARY OF THE INVENTION

The invention therefore provides, in a first embodiment, a molded detergent and cleaning product product comprising compressed detergent and cleaning particles.

-5 a composition comprising surfactant (s), activating additives, and optionally other detergent ingredients, wherein the shaped article further comprises:

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

b) 3 to 60 wt. an effervescent gas generating system.

Within the scope of the present invention, the contents of compositions a) or b) will be shortly referred to hereinafter as "component a) or" component b) ". In this context, the term 'ingredient' is to be understood only as a linguistic expression. In particular, the effervescent system (b) may consist of a plurality of compounds which do not necessarily exist in the form of a single compound. More likely, the total content of the compounds in question, which may also be in completely different raw materials or mixtures, is determined mathematically and is designated as' component (b) ^u . Likewise, the water-insoluble disintegrating aids in the form of a single component need not necessarily be swellable. Here too, where appropriate, several disintegrating aids of the abovementioned kind may exist in a wide variety of individual raw materials and / or mixtures, which are summarized as 'component (a)'.

Especially polymeric substances having a molecular weight of several tens of thousands up to hundreds of thousands of moles ¹ are used as swellable, water-insoluble disintegrants (component a)}. In addition to synthetic polymers such as polyvinylpyrrolidone and polyvinyl alcohol, natural and chemically modified biopolymers which can be selected, for example, from the group of alginates, starches and cellulose, are suitable as component a). Preference is given to selecting component a) from natural and synthetic polysaccharides and derivatives thereof.

These groups include, for example, pure polysaccharides - starches and cellulose, but also esterification or ether linkage products in which the hydroxy-hydrogen atoms have been substituted. However, celluloses or starches in which hydroxyl groups have been replaced by functional groups not bonded via an oxygen atom can also be used as a polysaccharide derivative. Cellulose derivatives include, for example, alkali celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers as well as aminocellulose, and starch derivatives include, for example, carboxymethyl starch (CMS).

Of course, both swellable, water-soluble disintegrant and microcrystalline cellulose can be used. This cellulose has a primary particle size of about 5 µm and can, for example, be compacted into granules with a mean particle size of 200 µm. Such compacts are stable and can be mixed with other substances without breaking into primary particles.

The swellable, water-soluble disintegrating aids can be used not only in the form of fine-grained powders, but also in the coarse form obtained in the spray-drying, granulation, agglomeration, compacting, pelleting or extrusion process. These "granular" disintegrants do not only include disintegrants in granular form, but also, for example, in co-granular or otherwise compacted form.

In a preferred detergent molding, 1 to 10 wt.%, More preferably 2 to 7 wt. % and in particular 3 to 5 wt. based on the total shaped cellulose or cellulose derivative.

The effervescent gas generating system (component (b)) may consist of a single compound which releases gas upon contact with water. Among these compounds, mention should be made of the magnesium peroxide mentioned above, which releases oxygen upon contact with water. Typically, however, the gas releasing effervescent system consists of at least two components which interact with each other to form a gas. While it is possible to implement a number of systems which, for example, release nitrogen, oxygen or hydrogen, it is possible to choose the effervescent system used for the molded articles of the detergent compositions of the invention based on both economic and environmental aspects. Preferred components b) consist of an alkali metal carbonate and / or alkali metal bicarbonate as well as an acidifying agent suitable for releasing carbon dioxide from the aqueous solution of alkali metal salts.

For alkali metal carbonates or alkali metal bicarbonates, sodium and potassium salts are considerably preferred over other salts for cost reasons. Of course, there is no need to use the pure alkali metal carbonates or alkali metal bicarbonates concerned; much more is

Advantageous from technical-washing interests is the use of mixtures of different carbonates and bicarbonates.

2 to 20% by weight, more preferably 3 to 15% by weight, are used as component b) in preferred detergent moldings. % and in particular 5 to 10 wt. % of an alkali metal carbonate or bicarbonate as well as 1 to 15, more preferably 2 to 12, and in particular 3 to 10 wt. of an acidifying agent, based on the total shaped article.

Suitable acidifying agents which release carbon dioxide from an aqueous solution of alkali salts include, for example, boric acid as well as alkali metal hydrogensulfates, alkali metal dihydrogen phosphates, and other inorganic salts. However, organic acidifying agents are preferred, with citric acid being a particularly preferred acidifying agent. However, other solid mono-, oligo- and polycarboxylic acids are also particularly useful. Of this group, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred. Organic sulfonic acids such as amidosulfonic acid are also useful. Commercially available and as acidifying agent in the context of the present invention are also preferably used Sokalan® DCS (trade mark BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max 50% by weight) and adipic acid (max. 33% by weight).

Preferred within the scope of the present invention are shaped laundry detergent compositions wherein the acidifying agent in component (b) is an organic di-, tri- and oligocarboxylic acid group or mixtures thereof.

The detergent moldings of the present invention preferably contain additionally additional laundry and detergent ingredients from the group of surfactants, builders, bleaches, bleach activators, enzymes, optical brighteners, foam inhibitors, perfumes and dyes. These substances will be described in detail.

Anionic, nonionic, cationic and / or amphoteric surfactants may be used in the shaped articles of the detergent and cleaning compositions of the present invention.

Advantageously, mixtures of anionic and nonionic surfactants are preferred from an application-technical point of view, and the proportion of anionic surfactants should be greater than that 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, a surfactant content of more than 15% by weight is preferred.

As anionic surfactants, for example, surfactants of the sulphonate and sulphate type are used. Particularly suitable surfactants of the sulfonate type are _Cg . _13- alkylbenzenesulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkanesulfonates as well as disulfonates such as those obtained from C ₁₂ , for example. _18- monoolefins with terminal and internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of sulfonation products. Also suitable are the alkanesulfonates obtained from _C12 . _18- alkanes, for example by sulfochlorination or sulfooxidation followed by hydrolysis or neutralization. Also suitable are esters of α-sulfofatty acids (estersulfonates), for example α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow.

Other suitable anionic surfactants are sulfated fatty acid glycerol esters. Glycerin esters of fatty acid are understood to be mono-, di- and triesters as well as mixtures thereof as obtained in the manufacture by esterification of one monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 moles of glycerin. Preferred sulfated fatty acid glycerol esters are the sulfated products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali metal and in particular sodium salts of sulfuric acid half esters C ₁₂ -C ₁₈ -fatty alcohols, such as coconut fatty alcohol, tallow alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₁₀ -C ₂₀ - oxoalcohols and semi-esters of secondary alcohols with this chain length. Further preferred are alk (en) ylsulphates of the stated chain length which contain a synthetic unbranched alkyl radical produced on a petrochemical basis, which are degraded as well as the corresponding fatty chemical compounds

-9surovín. To wash the art, preferred C ₁₂ -C ₁₈ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates. Suitable anionic surfactants are also 2,3-alkyl sulfates, which can be prepared, for example, in accordance with US Patent Application 3,234,258 or 5,075,041 and obtained as a sales product of Shell Oil Company under the name DAN®.

Monoesters of sulfuric acid and merozvetvených or branched C _{7th 21} alcohols ethoxylated with 1 to 6 moles of ethylene oxide, as well as 2-methyl-branched C8-alcohols with an average of 3.5 moles of ethylene oxide (EO) or _C12 . ₁₈ fatty alcohols with 1 to 4 EO. They are used in cleaning compositions only in relatively small amounts, for example in an amount of from 1 to 5 wt.

Other suitable anionic surfactants also include alkylsulfosuccinic acid salts, also referred to as sulfosuccinates or sulfosuccinic acid esters and the monoester and / or diester of sulfosuccinic acid with alcohols, more preferably fatty alcohols, and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ residues. _18- fatty alcohols or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol moiety which is derived from ethoxylated fatty alcohols, which themselves represent a nonionic surfactant (see description below). Here again, particularly preferred are sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrowed homolog distribution. It is also possible to use alk (en) ylsuccinic acid having in particular 8 to 18 carbon atoms in the alk (en) yl chain and salts thereof.

Suitable further anionic surfactants are, in particular, soaps. They are suitable

Saturated fatty acid soaps such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular mixtures of soaps derived from natural fatty acids, for example coconut, palm kernel or tallow.

The anionic surfactants, including soaps, exist in the form of their sodium, potassium or ammonium salts as well as the soluble salts of organic bases such as mono-, di- or triethanolamine. Preferred are anionic surfactants in the form of their sodium or potassium salts, especially in the form of the sodium salts.

As nonionic surfactants, especially alkoxylated, more preferably 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 moiety may be linear or more preferably in the 2-methyl position the branched chain may optionally contain a mixture of linear and methyl branched residues, as usually exists in oxoalcohol residues. However, alcohol ethoxylates having linear residues of alcohols of natural origin having 12 to 18 carbon atoms, such as coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol, are particularly preferred. Preferred ethoxylated alcohols include, for example, C ₁₂ . ₁₄ -alcohols with 3 EO or 4 EO, _{β β} . _η -alcohols 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, as mixtures of C ₁₂ . ₁₄ alcohols with 3 EO and C ₁₂₁₈ alcohols with 5 EO. The degrees of ethoxylation indicated are a statistical mean, which may be an integer or a fraction for a special product. Preferred alcohol ethoxylates have a narrowed distribution of homologs (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. An example for these is tallow alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, alkyl glycosides of the general formula RO (G) _X may be used as further nonionic surfactants, in which R is a primary unbranched or methyl branched, especially in the 2-position, a methyl branched aliphatic radical having 8 to 22, more preferably 12 to 18 carbon atoms and G is a symbol for a glycose unit having 5 or 6 carbon atoms, in particular for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number from 1 to 10, t, more preferably from 1.2 to 1.4.

Another class of nonionic surfactants used which are used either as a single nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, in particular ethoxylated or ethoxylated and propoxylated alkyl esters of fatty acids, in particular of 1 to 4 carbon atoms in the alkyl chain, in particular methyl ester of fatty acids. as described in Japanese Patent Application JP 58/217598 or more preferably produced according to the procedure described in International Patent Application WO-A-90/13533.

Nonionic surfactants of the amine oxide type may also be suitable, for example, N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the type of fatty acid alkanolamides. The preferred amount of these nonionic surfactants is not more than the amount of ethoxylated fatty alcohols, especially not more than half.

Other suitable surfactants are the polyhydroxy fatty acid amides of formula (D.

R ¹

I

R-CO-N- [Z] (I) wherein RCO is an aliphatic acyl radical of 6 to 22 carbon atoms, R ¹ is hydrogen, an alkyl or hydroxyalkyl radical of 1 to 4 carbon atoms, and [Z] is a linear or branched poly hydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can be obtained in a conventional manner by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, an alkyl ester of a fatty acid or a fatty acid chloride.

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

R ¹ -OR ²

I

R-CO-N- [Z] (II) wherein R represents a linear or branched alkyl or alkenyl radical of 7 to 12 carbon atoms, R ¹ is a linear, branched or cyclic alkyl radical or an aryl radical of 2 to 8 carbon atoms, and R ² is a linear, branched, or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or C _1-4 alkyl being preferred;

-12-phenyl radicals and [Z] means a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups or alkoxylated, in particular ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably obtained by reductive amination of a reducing sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. These N-alkoxy or N-aryioxy-substituted compounds can then be converted, for example, according to the teaching of International Patent Application WO-A-95/07331 by reaction of fatty acid methyl esters in the presence of an alkoxide catalyst to the desired polyhydroxy fatty acid amides.

Skeleton substances which may be included in the detergent articles according to the invention are, in particular, silicates, aluminum silicates (zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures thereof.

Suitable crystalline, layered sodium silicates have the general formula NaMSixOjx + pHjO, 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 values for x 2, 3 or 4 are preferred. layer silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layer silicates of the formula are those in which M is sodium and x is 2 or 3. Particularly preferred are both β- and δ-sodium silicates Na ₂ Si ₂ O ₅ yH ₂ O, wherein sodium β-disilicate can be obtained, for example, by the procedure described in International Patent Application WO-A-91/08171.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, more preferably from 1: 2 to 1: 2.8, and in particular from 1: 2 to 1: 2.6, are also useful. they dissolve late and have secondary washing properties. Delayed dissolution over conventional amorphous sodium silicates can be caused by a variety of methods, such as surface treatment, compounding, compacting / compacting, or drying. Within the scope of the present invention, the term "amorphous" also means "X-ray amorphous". That is, silicates do not cause sharp X-ray reflections in X-ray diffraction experiments, as is typical of crystalline substances, but in all cases one or more maxima of the dispersed X-ray diffraction.

-13 irradiations having a width of several degrees of bending angle. However, when silicate particles provide blurred or even sharp bending maxima in electron diffraction experiments, they may even have very good activating additive properties. This should be interpreted as meaning that the products have microcrystalline regions with a size of 10 to several hundred nm, values up to a maximum of 50 nm and in particular up to 20 nm being preferred. Such so-called x-ray amorphous silicates, which dissolve equally delayed in comparison to conventional waterglasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and dried silica amorphites are particularly preferred.

Preferred is the use of finely crystalline, synthetic zeolite containing bound water, zeolite A and / or P. As zeolite P, zeolite MAP® (sold by Crosfield) is particularly preferred. However, zeolite X as well as mixtures of A, X and / or P are also suitable. The zeolite can be used as a spray-dried powder or as a non-dried, stabilized suspension which is still wet. When the zeolite is used as a suspension, it may contain small amounts of additives, nonionic surfactants as stabilizers, for example 1 to 3 wt. based on zeolite, ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups, C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups, or ethoxylated isotridecanols. Suitable zeolites have a mean particle size of less than 10 µm (Volume Distribution: Coulter Counter) and preferably contain 18 to 22 wt%, especially 20 to 22 wt%. bound water.

Of course, it is also possible to use the commonly known phosphates as activating additives, unless such use is to be avoided for ecological reasons. Sodium salts of orthophosphates, pyrophosphates and especially tripolyphosphates are particularly suitable.

Useful organic constituents of the skeleton are, for example, polycarboxylic acids 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), unless it is necessary to object to their use. for ecological reasons, as well as mixtures thereof. Preferred are

Salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, and mixtures thereof. These salts are used because of their skeletal properties and cannot be considered as part of an effervescent system if the salts are not suitable, for example, to release carbon dioxide from bicarbonate.

Among the compounds providing a water H ₂ O ₂ serve as bleaching agents are as in particular sodium perborate tetrahydrate and sodium perborate monohydrate. Other useful bleaching agents are, for example, sodium percarbonate, peroxy pyrophosphates, citran peroxyhydrates as well as peroxyacid salts or peroxyacids providing H ₂ O ₂ , such as perbenzoates, peroxophthalanes, diperoxyazelaic acid, phthaliminoic peroxyacid or diperoxydodecanoic diacid.

In order to achieve an improved bleaching effect at washing temperatures of 60 ° C and below, it is possible to incorporate the bleach activator as a separate component or as a component of component b). Bleach activators which may be used are compounds which give, under perhydrolysis conditions, aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acids. Compounds having O- and / or N-acyl groups with the indicated number of carbon atoms and / or optionally substituted benzoyl groups are suitable. Preferred are multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenolsulphonates, in particular n-nonanoyl- or isononanoyloxybenzenesulphonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triethylethic alcohols, ethyl triacetate, ethyl ether , 5-diacetoxy-2,5-dihydrofuran.

In addition to or in place of conventional bleach activators, so-called bleach catalysts can be incorporated into shaped articles. These substances are transition metal salts or bleach-enhancing transition metal complexes such as Μη-, Fe-, Co-, Ru- or Mo-salt.

-15 complexes or -carbonyl complexes. Also useful as bleach catalysts are Μη-, Fe-, Co-, Ru-, Mo-, Ti-, V- or Cu-complexes with a nitrogen-containing tripod ligand as well as Co-, Fe-, Cu-Ru-amine complexes.

Suitable suds inhibitors which may be components of component b) or which may be employed as components b) themselves are, for example, soaps of natural or synthetic origin having a high proportion of _C18 . ₂₄ fatty acids. Suitable non-surfactant suds inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silicic acid or bistearylethylenediamide. Mixtures of various suds inhibitors, such as those of silicones, paraffins or waxes, are also preferably used. It is preferred to bind the suds inhibitors in a granular, water-soluble or dispersible carrier. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

In addition, molded detergent products may also contain ingredients that have a positive effect on the washing of oils and fats from textiles (so-called soil beet only). This effect is particularly pronounced when soiling a fabric which has been washed several times with a detergent according to the invention which contains these oil- and fat-dissolving components. Preferred oils and fat solubilizers include, for example, nonionic cellulose esters such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of from 15 to 30% by weight. % and hydroxypropoxy groups of from 1 to 15 wt. in each case based on the nonionic cellulose ester as well as polymers of phthalic acid and / or terephthalic acid or derivatives thereof known in the art, in particular polymers of ethylene terephthalanes and / or polyethylene glycol terephthalanes or their anionically or nonionically modified derivatives. Of these, 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. Particularly suitable are enzymatic active substances obtained from strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus. Preference is given to the use of Subtilisin-type proteases and in particular to proteases derived from Bacillus lentus. Of particular importance here are mixtures of enzymes,

For example, proteases and amylases or proteases and lipases or proteases and cellulases or cellulases and lipases or proteases, amylases and lipases or proteases, lipases and cellulases, in particular mixtures containing cellulase. In several cases, peroxidases or oxidases have also proven suitable. The enzymes may be adsorbed onto the support and / or stored in packaging materials to protect them against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules in the shaped articles according to the invention can be, for example, from 0.1 to 5% by weight, in particular from 0.1 to about 2% by weight.

The shaped articles may contain as optical brighteners derivatives of diamine-stendenedisulfonic acid or alkali metal salts thereof. Suitable salts are, for example, 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid salts or compounds of the same type which have morpholine instead of morpholine. a diethanolamine group, a methylamine group, an aniline group or a 2-methoxyethylamine group. Substituted diphenylstyryl-type brighteners may also be present, for example 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) -difenyIu. It is also possible to use mixtures of the said brighteners.

In a further embodiment, the invention relates to processes for the production of the detergent moldings according to the invention by molding detergent / detergent particles comprising surfactant (s), activating additives as well as optionally other detergent / detergent ingredients, wherein the detergent / detergent composition for compression further includes:

a) 1 to 10 wt. one or more swellable water-insoluble disintegrating aids; and

b) 3 to 60 wt. a gas generating effervescent system, in each case based on the resulting shaped article, whereby components a) and / or b) can be mixed with the other components of the detergent and cleaning agent contents in a compounded manner as well as separately.

The masterbatch of particles to be compressed may exist as a pure powder mixture containing components a) and b), but it is preferred that the individual raw materials are

The mixture is already processed, in particular compacted form. In particular, the disintegrating aids are added to the masterbatch in the form of granules, pellets, compacts or extrudates. The same also applies to certain other ingredients such as surfactants, which are advantageously added to the masterbatch in the form of particles containing activating additives which have been obtained by spray drying, granulation, pelleting, compacting or extrusion.

In preferred embodiments of the process of the invention, the detergent composition particles are compressed at temperatures below 30 ° C and with a compression pressure of less than 15 N / cm ² . The actual production of the shaped articles according to the invention takes place first by dry mixing of the components, which may be wholly or partially pre-granulated, and subsequent molding, in particular tablet compression, using a conventional method (e.g. as described in conventional tableting patent literature, particularly in the field). detergents or cleaning agents, in particular in the aforementioned patent applications and the article "Tableting: State of the Art", S ,FW-Journal, 122th edition, pages 1016-1021 (1996)).

The shaped articles can be produced in a given spatial shape and a certain size. As a spatial shape, practically all meaningfully manageable shapes are possible, for example in the form of sheets, rods or bars, cubes, blocks and corresponding spatial shapes with planar faces, and in particular cylindrical shapes with a circular or oval cross-section. The latter shape comprises embodiments of the tablet up to compact cylinders having a height to diameter ratio of greater than 1.

In this case, the moldings may be designed as separate elements which are separate from one another and which correspond to a specified amount of detergent and / or cleaning agent dosing. However, it is also possible to make the compacts such that a plurality of such units of mass are combined into a single compact, while ensuring that the smaller portioned portions are easily separated by designated fracture points. For the use of textile laundry detergents in machines of common types in Europe with horizontally arranged mechanics, it may be expedient to make portions in the form of tablets, cylindrical or cuboid, with a preferred diameter ratio

-18 to a height ranging from about 0.5: 2 to 2: 0.5. Conventional hydraulic presses, eccentric presses or carousel presses are particularly suitable for the production of such pressings.

The spatial shape of another embodiment of the shaped article is in its dimensions adapted to the hopper of a commercially available household washing machine so that it is possible to insert the shaped article without dosing aids directly into the hopper where it dissolves during the soaking. Of course, however, the use of detergent shaped articles by means of dispensing aids is also problem-free and advantageous within the scope of the present invention.

Another preferred molded article that can be produced has a plate or plate structure with alternately thick long and thin short segments, so that it is possible to break off the individual segments from this "table" at designated fracture points that represent short thin segments and insert them into machine. This principle of "tabular" shaped detergent articles can also be carried out in other geometric forms, for example as vertical standing triangles, which are connected longitudinally to one another only on one of their sides.

However, it is also possible that the various components are not compressed into a single tablet, but rather a molded product with several layers, i.e. at least two layers, is obtained. It is also possible for the different layers to have different dissolution rates. This can result in advantageous user-technical properties of the shaped article. In the case of components that have a negative effect on each other in the molded article, it is possible to integrate one component into the faster soluble layer and incorporate another component into the slower soluble layer so that the first component has already reacted when the second is in solution. The arrangement of the layers in the molded article may also be stacked, whereby the process of dissolving the inner layer (s) at the edges of the molded article already takes place when the outer layers have not yet been completely dissolved, but a full coating of the inner layer (s) can be achieved. the underlying layer (s), thereby preventing premature dissolution of the components of the inner layer (s).

In a further preferred embodiment of the invention, the shaped article consists of at least three layers, i.e. two outer layers and at least one inner layer, wherein at least one of the inner layers comprises a peroxide

The bleaching agent, while for the stacked molded article, both the outer layers and the coated molded article, the outer layers do not contain a peroxide bleaching agent. It is furthermore possible to spatially separate the peroxide bleaching agent and any bleach activators and / or enzymes present in the shaped article; Such multilayer shaped articles have the advantage that they do not need to be inserted into the water bath only by means of a hopper or dispensing device; much more, in such cases, it is also possible to bring the molded article into direct contact with the fabric in the washing machine without having to worry about staining with bleaching agents and the like.

Similar effects can also be achieved by coating the individual components of the laundry detergent compositions or the entire molded article. For this purpose, shaped articles to be coated may be sprayed with aqueous solutions or emulsions or coated by a fusion coating process.

The shaped articles of the invention, in particular such poorly disintegrating and poorly soluble detergent shaped articles and bleached shaped articles, have excellent disintegration properties due to the water-insoluble, swellable disintegrant and effervescent system (components a) and b). This can be tested, for example, under critical conditions in conventional household washing machines (use directly in the water bath using a conventional dispenser, washing program for delicate or colored laundry, washing temperature max. 40 ° C).

Thus, in another embodiment of the invention, a washing process is required, wherein the shaped article is inserted into a water bath through a household washing machine chute. The dissolution times of the molded article in the washing machine are less than 8 minutes and in particular less than 5 minutes. A further embodiment of the invention requires a washing process in which the shaped article is inserted - possibly by means of a dosing device - directly to the laundry contained in the household washing machine drum. Here, the shaped article can advantageously be inserted directly i.e. without additional laundry dispenser; use of known dosing

However, devices such as bags, sachets, plastic containers or the like are equally problem-free.

DETAILED DESCRIPTION OF THE INVENTION

Molded detergent articles according to the invention 1 and 2 as well as comparative examples 3 and 4 having the composition according to Table 1 were produced by molding the detergent particles.

The comparative examples do not contain either component a) (example 3) or component b) (example 4), with a small amount of Na ₂ CO _{3 being} used as the skeleton substance.

Table 1: Molded detergent products [wt%]

Shaped washing and cleaning products funds 1 2 3 4 C ₉ . _13- alkylbenzenesulfonate 11.4 10,0 10.6 10,0 sulphate C ₁₂ . _18- fatty alcohol - 6.6 2.4 6.8 C ₁₂ . _18- fatty alcohol with 7 EO 5.8 - 4.8 6.2 soap 0.7 2.1 1.6 1.8 nátriumtripolyfosforečnan - 23.5 - - zeolite 4A (based on anhydrous substance) 18.5 3.5 20.0 20.0 sodium perborate 18.2 - 18.6 18.6 sodium percarbonate - 23.0 - - tetraacetylethylenediamine (TAED) 6.4 3.4 5.8 5.8 cellulose (component a)} 3.4 4.0 - 6.0 citric acid (substance of component b)} * 3.2 3.5 3.5 - Na ₂ CO ₃ (substance of component b)} * 8.6 - 8.1 6.3 NaHCO ₃ (substance of component b)} * 6.4 7.0 6.8 - amorphous sodium silicate 3.3 2.1 3.0 3.4

-21 Table 1 - continued

Shaped washing and cleaning products funds 1 2 3 4 acrylic acid copolymer - acid maleic 2.7 2.5 2.5 2.6 enzymes 2.3 4.0 2.7 2.7 brighteners 0.2 0.2 0.2 0.2 polyethylene glycol (molar mass approx. 4000 g / mol) 0.5 salt / water Rest Rest Rest Rest

* mixed separately

The hardness of the tablets was measured by deformation of the tablet up to the break, with the force acting on the sides of the tablet and determining the maximum force the tablet could withstand.

To determine the disintegration of the tablet, the tablet was placed in a beaker of water (600 ml of water, temperature 30 ° C) and the time to complete disintegration of the tablet was measured.

For the loading test, 3 tablets of 40 g were placed in the receiving chamber of the washing machine. After the impregnation process, the residue in the chamber was dried and weighed.

Table 2 shows the experimental data:

Table 2: Detergent tablets [physical data]

tablet Example 1 Example 2 Example 3 Example 4 tablet hardness 33 N 25 N 30 - 35 N 30 - 35 N tablet disintegration 5- 10s 5-10s > 5 min 2 min Rest - - 34 g I2G

Claims (9)

PATENT CLAIMS 1. Detergent-shaped moldings of compressed detergent-detergent particles containing surfactant (s), activating additives, and optionally other detergent-containing components, characterized in that the molded product further comprises: a) 1 to 10 wt. one or more swellable, water-insoluble disintegrating aids converted into coarse form by spray-drying, granulation, agglomeration, compacting, pelleting or extrusion, and b) 3 to 60 wt. an effervescent gas generating system. 2. The detergent article according to claim 1, wherein component (a) is selected from natural and synthetic polysaccharides and derivatives thereof. I Shaped detergent products according to one of claims 1 or 2, characterized in that component b) consists of an alkali metal carbonate and / or alkali metal bicarbonate and an acidifying agent suitable for releasing carbon dioxide from salts. alkali metals in aqueous solution. Molded detergent products according to one of Claims 1 to 3, characterized in that from 1 to 10% by weight, more preferably from 2 to 7% by weight, is used as component (a). % and in particular 3 to 5 wt. based on the total shaped cellulose or cellulose derivative. Molded detergent products according to one of Claims 1 to 4, characterized in that 2 to 20% by weight, more preferably 3 to 15% by weight, is used as component b). % and in particular 5 to 10 wt. an alkali metal carbonate or bicarbonate as well as 1 to 15, more preferably 2 to 12; %, In particular 3 to 10 wt. of an acidifying agent, based on the total shaped article. Washing and cleaning compositions according to one of Claims 3 to 5, characterized in that a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof is used as the acidifying agent in component b). 7. A process for producing detergent moldings by molding detergent / detergent particles containing surfactant (s), activating additives, and optionally other detergent / detergent ingredients, characterized in that the detergent / detergent to be pressed further comprises: : a) 1 to 10 wt. one or more swellable, water-insoluble disintegrating aids converted into coarse form by spray-drying, granulation, agglomeration, compacting, pelleting or extrusion, and b) 3 to 60 wt. a gas generating effervescent system, in each case based on the resulting shaped article, whereby components a) and / or b) can be mixed with the other components of the detergent and cleaning agent contents in a compounded manner as well as separately. Method according to claim 7, characterized in that the compacting of the detergent / cleaning composition particles is carried out at temperatures below 30 ° C and with a compression pressure of less than 15 N / cm ² . Washing method using a shaped article according to one of claims 1 to 6, characterized in that the shaped article is inserted into a water bath through a household washing machine chute. -2410. Washing method using a shaped article according to one of claims 1 to 6, characterized in that the shaped article is inserted directly to the laundry into a household washing machine drum.