WO1998035011A1 - Use of additives containing co-builders in detergents and cleaning agents - Google Patents

Abstract

The invention relates to an additive for use in detergents or cleaning agents, having a polyfunctional but at least bifunctional effect in the washing or cleaning solution by helping to soften the solution and promoting foam formation, and containing bicarbonate and organic polycarboxylic acids. According to the invention, the additive also contains an additional raw material or compound, which is present in its solid state at a pressure of 1 bar and at temperatures below 45 DEG C, but at processing conditions is present in liquid form and in said liquid form serves as a water-soluble binder. According to the invention, the quantity of bicarbonate, organic polycarboxylic acids and binder contained in the additives is at least 60 weight percent and the quantity of tensides between 0 and less than 5 weight percent. Of particular benefit is the use of additives containing between 80 and 100 weight percent bicarbonate, organic polycarboxylic acid and binder and between 0 and 5 weight percent tensides, preference being given to a tenside-free additive. A preferred form of detergents or cleaning agents containing such additives present only very little residue.

Description

 Use of additives containing cobuilder in detergents or cleaning agents

The invention relates to the use of cobuilder-containing additives in washing or cleaning agents, which not only has a very good dissolving behavior and contributes to the rapid softening of the washing or cleaning liquor, but also improves the washing-in behavior of washing or cleaning agents. In addition, the agent promotes foam formation and thus contributes to the gentle cleaning of textiles in the wash liquor. Corresponding washing or cleaning agents have a low residue behavior.

The prior art already knows several additives for detergents or cleaning agents, which as components include also contain alkali metal carbonates or alkali metal bicarbonates and organic acids such as citric acid.

For example, the European patent application EP-A-0 737 738 (Cleantabs) describes a percarbonate-containing tablet which additionally contains 5 to 35% by weight of citric acid and optionally also up to 25% by weight of bicarbonate and up to 8% by weight. -% may contain polyethylene glycols.

German patent application DE-A-42 03 169 (BASF) describes a bleach activator granulate containing benzoxazinone derivatives and 2 to 70% by weight of other conventional constituents, which include, for example, surfactants, but also polymers, polysaccharides, polyalkylene glycols, neutral, alkaline or acidic salts of inorganic acids and organic carboxylic acids are counted.

Japanese patent application JP-A-02/255800 (Kao) also discloses bleach activator granules with bleach activator contents of 10 to 85% by weight. Non-ionic surfactants, polyethylene glycol, citric acid and bicarbonate are mentioned as further ingredients.

Japanese patent application JP-A-58/213714 (Kao) discloses washing or cleaning tablets, also bathroom cleaners, which contain bicarbonate, polyethylene glycols with a molecular weight between 2000 and 10000 and polycarboxylic acids. The bicarbonate is first mixed with the polyethylene glycol, melted at temperatures between 60 and 100 ° C., then cooled, pulverized, mixed with the polycarboxylic acid, in particular citric acid, and then pressed. Such Tablets produced are free of chipping (deterioration of the appearance of the surfaces due to depressions).

The German patent application DE-A-38 25 317 (Lab. Hausmann), on the other hand, describes powders or tablets which are used as contact lens cleaners and which, in addition to hydrogen peroxide and manganese EDTA, contain above all alkali metal bicarbonate, citric acid and polyethylene glycol with a relative molecular weight of 6000.

Japanese laid-open patent publication JP 04/100900 describes foaming bath additives or disinfectants, with a foaming component B to ensure that the actually essential component A is evenly distributed in the wash water.

None of the cited prior art documents describes the use of powdery to granular additives for use in detergents or cleaning agents which, in addition to softening the water in the washing or cleaning liquor, also promote the formation of foam.

The object of the invention was to provide an additive for use in detergents or cleaning agents which has a polyfunctional, or at least bifunctional, effect in the washing or cleaning liquor by contributing to water softening of the liquor and to promoting foam formation in the liquor .

The invention thus relates in a first embodiment to the use of a powdery to granular additive for use in detergents or cleaning agents for softening the water in the washing or cleaning liquor and at the same time promoting foam formation in the liquor containing bicarbonate and organic polycarboxylic acids, the invention additionally comprising Raw material or compound which is present in solid form at a pressure of 1 bar and temperatures below 45 ° C, but is present as a melt under the processing conditions, this melt serving as a water-soluble binder is contained, with the proviso that the bicarbonate, organic polycarboxylic acid and binder content of the additives is at least 60% by weight and the additive contains surfactants in amounts from 0 to below 5% by weight.

Such additives can be used both in washing or cleaning agents for mechanical and for manual use. Especially in machine Detergent foam formation helps to mitigate the negative effects of the washing machine mechanics on high-quality textiles in particular. This results in a gentler cleaning of the textiles.

With regard to manual washing or cleaning agents, in particular for hand washing agents or for cleaning agents for hard surfaces, it is generally desirable to promote foam formation. The positive effects of an additive according to the invention or an inventive use of such additives in manual use are thus obvious.

The additives used according to the invention have an excellent dissolving behavior in water and thus contribute to improving the washing-in behavior of detergents or cleaning agents for machine use.

Depending on their production, the powdery to granular additives can have bulk densities between about 300 and 800 g / l. The bulk density is advantageously adapted to the desired bulk density of the washing or cleaning agent. A preferred method of making these additives is described below.

The essential ingredients of the additive are bicarbonate, organic polycarboxylic acid and the binder as defined above.

Both sodium bicarbonate and potassium bicarbonate can be contained in the additive as bicarbonate, although sodium bicarbonate is preferred. The bicarbonate content of the additives is preferably more than 30% by weight and, in particularly advantageous embodiments, is even significantly above 40% by weight.

Organic polycarboxylic acids which can be used are those which, or their salts, are usually present in washing or cleaning agents as organic builders or cobuilders. These include, for example, citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, and mixtures of these. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof, but in particular citric acid and optionally mixtures of citric acid with other polycarboxylic acids, are to be mentioned as preferred. In principle, (co) polymeric polycarboxylic acids such as poly lyacrylic acid, polymaleic acid or copolymers of acrylic acid, maleic anhydride and optionally vinyl acetate under this definition. From today's perspective, however, the use of these (co) polymeric polycarboxylic acids is clearly less preferred.

The organic polycarboxylic acids are preferably present in the additives in amounts of 20 to 50% by weight, a particularly preferred embodiment of the invention providing that the content of bicarbonate in the additive is always greater than the content of organic polycarboxylic acid. It has proven to be particularly advantageous if the additive contains sodium bicarbonate and citric acid in a molar ratio of about 3: 1, a ratio of 3.5: 1 being quite preferred, while a ratio of 2.5: 1 is considered less advantageous .

The third essential ingredient of the additives is a raw material or a compound which serves as a binder, although it is solid at room temperature, but is present in liquid form in the form of a melt under the process conditions. The binder itself can either be melted onto the premix containing bicarbonate and organic polycarboxylic acid, sprayed on or added dropwise to this premix. On the other hand, it has also proven to be advantageous to introduce the binder in solid form as a powder into the premix. The melting point or softening point at a pressure of 1 bar is at least 45 ° C. and (in particular for economic reasons) preferably below 200 ° C., in particular below 150 ° C. If the binder is introduced into the premix in the form of a melt, the temperature in the melting vessel is also more than 45 ° C. to a maximum of about 200 ° C., the temperature in the melting vessel being the melting temperature or the temperature of the softening point of the binder or can exceed the binder mixture significantly.

If a binder with a high melting point or high softening point is selected, a temperature must be set in the processing step which ensures that the binder melts. On the other hand, the lower limit for the melting point or softening point is of great importance, since at melting points or softening points below 45 ° C, an end product is usually obtained which is already at room temperature and slightly elevated temperatures of around 30 ° C tends to stick in summer temperatures and under storage or transport conditions. It has proven to be particularly advantageous if a few degrees, for example 2 to 20 ° C., are used above the melting point or above the softening point. In a preferred embodiment of the invention, a binder is used which is already completely in the form of a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C. The binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.

Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols. The modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000. Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000. For a more detailed description of the modified polyalkylene glycol ethers, reference is made to the disclosure of the international patent application WO-A-93/02176. In the context of this invention, polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C ₃ -C ₅ glycols and glycerol and mixtures of these as starting molecules. Ethoxylated derivatives such as trimethylo-propane with 5 to 30 EO are also included.

The polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred.

The particularly preferred polyethylene glycols include those with relative molecular weights of up to 12,000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4000, and such combinations advantageously of more than 50 % By weight, based on the total amount of the polyethylene glycols, have polyethylene glycols with a relative molecular weight between 3500 and 5000. However, polyethylene glycols which are in liquid form at room temperature and under a pressure of 1 bar can also be used as binders; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one other binder, this mixture again having to meet the requirements of the invention, must have a melting point or softening point of at least above 45 ° C.

Anhydrous, swollen polymers have also proven to be advantageous binders, as are described, for example, in the older, unpublished German patent application 197 53 310.8.

Likewise suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as sole binders, but in combination with others, in particular in combination with Polyethylene glycols used.

Other suitable binders have also been found to be raw materials with washing or cleaning properties, for example nonionic surfactants with melting points of at least 45 ° C. or mixtures of nonionic surfactants and other binders. It should be noted here, however, that the total surfactant content of the additives should be less than 5% by weight. The preferred nonionic surfactants include alkoxylated fatty or oxo alcohols, in particular C ₁₂ -C ₁₈ alcohols. Here, degrees of alkoxylation, in particular degrees of ethoxylation, of on average 18 to 80 AO, in particular EO per mole of alcohol and mixtures thereof have proven to be particularly advantageous. In particular, fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO, show advantageous binder properties in the sense of the present invention. Binder mixtures may also contain ethoxylated alcohols with an average of fewer EO units per mole of alcohol, for example tallow fatty alcohol with 14 EO. However, it is preferred to use these relatively low ethoxylated alcohols only in a mixture with higher ethoxylated alcohols. Advantageously, the content of these relatively low ethoxylated alcohols in the binders is less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used. In particular, nonionic surfactants such as C ₁₂ -C ₁₈ alcohols with an average of 3 to 7 EO, which are usually used in washing or cleaning agents and which are liquid per se at room temperature, are preferably only present in the binder mixtures in such an amount that less than 2 % By weight of these nonionic surfactants, based on the additive, are provided. As already described above, however, it is less preferred to use nonionic surfactants which are liquid at room temperature in the binder mixtures. In a particularly advantageous embodiment such nonionic surfactants are not a component of the binder mixture, since they not only lower the softening point of the mixture, but can also contribute to the stickiness of the additive and also, because of their tendency to cause gelation when in contact with water, also the requirement for the quick dissolution of the additive could counteract. Likewise, it is not preferred that conventional anionic surfactants or their precursors, the anionic surfactant acids, used in washing or cleaning agents are contained in the binder mixture.

Other nonionic surfactants which are suitable as binders are the fatty acid methyl ester ethoxylates which do not tend to gel, in particular those with an average of 10 to 25 EO (for a more detailed description of this group of substances, see below). Particularly preferred representatives of this group of substances are predominantly methyl esters based on C ₁₆ -C ₁₈ fatty acids, for example hardened beef tallow methyl esters with an average of 12 EO or with an average of 20 EO.

In a preferred embodiment of the invention, a mixture is used as the binder which uses C ₁₂ -C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol with a relative molecular weight of 400 to 4000.

In a further preferred embodiment of the invention, a mixture is used as the binder which is predominantly methyl ester-based C ₁₆ -C ₁₈ fatty acids with an average of 10 to 25 EO, in particular hardened beef tallow methyl ester with an average of 12 EO or an average of 20 EO, and a C ₁₂ - Contains C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO and / or polyethylene glycol with a relative molecular weight of 400 to 4000.

Particularly advantageous embodiments of the invention have been found to be binders based either solely on polyethylene glycols with a relative molecular weight of around 4000 or around 6000 or on a mixture of C ₁₂ -C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO and one of the above described fatty acid methyl ester ethoxylates or on a mixture of C ₁₂ -C ₁₈ fatty alcohol based on coconut or tallow with an average of 20 EO, one of the fatty acid methyl ester ethoxylates described above and a polyethylene glycol, in particular with a relative molecular weight around 4000. Other suitable binders are trimethylolpropylene etc. (commercial products from BASF, Federal Republic of Germany).

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further binders, alone or in combination with other binders, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 means carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. Alkyl glycosides which have a degree of softening above 80 ° C. and a melting point above 140 ° C. are particularly suitable. Highly concentrated compounds with contents of at least 70% by weight alkyl glycosides, preferably at least 80% by weight alkyl glycosides, are also suitable. Using high shear forces, the melt agglomeration and in particular the melt extrusion with such highly concentrated compounds can already be carried out at temperatures which are above the softening point but still below the melting temperature. Although alkyl glycosides can also be used as the sole binder, it is preferred to use mixtures of alkyl glycosides and other binders. In particular, here are mixtures of polyethylene glycols and alkyl glycosides, advantageously in weight ratios from 25: 1 to 1: 5, with particular preference from 10: 1 to 2: 1.

Also suitable as binders, in particular in combination with polyethylene glycols and / or alkyl glycosides, are polyhydroxy fatty acid amides of the formula (I) in which R ^ CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^ for hydrogen, an alkyl or hydroxyalkyl radical with 1 up to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

R ¹ -CO-N- [Z] (I)

The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

R ⁴ -OR ⁵

(II)

R ^J -CO-N- [Z]

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, where C _| -C ₄ alkyl or phenyl radicals are preferred, and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated, derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as 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 patent 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. Particularly preferred glucamides already melt at 95 to 105 ° C. But here too - as with the alkyl glycosides - working temperatures which are above the softening temperature but below the melting temperature are normally sufficient in the process according to the invention.

The content of binder or binders in the additive is preferably 5 to 15% by weight, in particular 7 to 12% by weight. In a preferred embodiment of the invention, no surfactants are used as binders, so that surfactant-free additives are used in a preferred embodiment of the invention. Preferred binders are polyalkylene glycols, in particular polyethylene glycols with a relative molecular weight above 2000, especially with a relative molecular weight of 4000 or 6000.

A preferred embodiment of the invention provides that the bicarbonate, organic polycarboxylic acid and binder content of the additives is above 65% by weight.

Other constituents of this additive can be conventional ingredients of detergents or cleaning agents (with the proviso that the surfactant content is less than 5% by weight), for example bleach activators and / or bleach catalysts, as well as colorants and or fragrances. 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. Preferred are polyacylated 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-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetic acid, especially triac 5-diacetoxy-2,5-dihydrofuran and the enol esters known from the German patent applications DE-A-196 16 693 and DE-A-196 16 767 as well as acetylated sorbitol and mannitol or those in European patent application EP-A-0 525 239 described mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, given if N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498 are known. The hydrophilically substituted acylacetals known from German patent application DE-A-196 16 769 and the acyl lactams described in German patent application DE-A-196 16 770 and international patent application WO-A-95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used.

The bleach activator can be coated with coating substances in a known manner or, if appropriate using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, may have been granulated or extruded / pelleted and, if desired, contain further additives, for example dye. Such granules preferably contain more than 70% by weight, in particular 90 to 99% by weight, of bleach activator. A bleach activator is preferably used which forms peracetic acid under washing conditions.

In addition to the conventional bleach activators listed above or in their place The sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from the European patents EP-A-0 446 982 and EP-A-0 453 003 can also be included as so-called bleaching catalysts. The transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum salen complexes known from German patent application DE-A-195 29 905 and their N- known from German patent application DE-A-196 20 267. Analog compounds, the manganese, iron, cobalt, ruthenium or molybdenum-carbonyl complexes known from German patent application DE-A-195 36 082, the manganese, iron described in German patent application DE-A-196 05 688 -, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium known from German patent application DE-A-196 20 411 Ammine complexes, the manganese, copper and cobalt complexes described in German patent application DE-A-44 16 438, the cobalt complexes described in European patent application EP-A-0 272 030, which result from European patent application EP-A -0 693 550 known Manganese complexes, the manganese, iron, cobalt and copper complexes known from European patent EP-A-0 392 592 and / or those described in European patent EP-A-0 443 651 or European patent applications EP -A-0 458 397, EP-A-0 458 398, EP-A-0 549 271, EP-A-0 549 272, EP-A-0 544 490 and EP-A-0 544 519 described manganese complexes . Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO-A-95/27775.

Bleach activators and / or bleach catalysts are preferably used in amounts of 5 to 35% by weight, in particular up to a maximum of 30% by weight, since the dissolving behavior of the additives is adversely affected by the bleach activators and catalysts.

For the above reason, in a particularly advantageous embodiment of the invention, additives are used in washing or cleaning agents which contain only small amounts of bleach activators and / or bleach catalysts. If particular attention is paid to the dissolving behavior and the residue behavior of the additives, it is preferred that the additives are free from bleach activators and / or bleach catalysts. These additives consist of 80 to 100% by weight, in particular 90 to 100% by weight, of bicarbonate, organic African polycarboxylic acid and a binder as defined above and 0 to 5% by weight of surfactants, surfactant-free additives being preferred.

An advantageous embodiment of the invention provides that the additives used according to the invention 2 to 10 wt .-%, in particular 3 to 8 wt .-% fragrances and / or dyes in amounts below 1 wt .-%, preferably as a solution in a polyethylene glycol with a molecular weight below 1000 or processed in the binder melt. Such additives have a very quick dissolving behavior and therefore cause the fragrance to spread quickly.

The additives for use in accordance with the invention are preferably produced in a mixer which is suitable for melt granulation or a coating process with a melt, or by granulation in a fluidized bed. The person skilled in the art knows a large number of mixers and fluidized bed devices in which such additives can be produced. It is essential that the binder is either already used in the form of a melt or that the processing temperature is set to such temperatures that the binder melts or at least softens plastically.

The powdery to granular additives are preferably used in washing or cleaning agents in amounts of 3 to 10% by weight.

In a further embodiment of the invention, a washing or cleaning agent is claimed which contains a powdery to granular additive as an admixture component, which contains bicarbonate, organic polycarboxylic acids and a binder as defined above, the additive having a content of these three ingredients of at least 60% by weight .-%. The additive only has surfactants in amounts of 0 to 5% by weight. Such additives have a residue (measured according to the residue test) of at most 10% by weight. The agents according to the invention are particularly suitable as hand washing agents for textiles, as foaming all-purpose cleaners or bathroom cleaners and as machine washing agents for delicates, wool and the like. The additives are preferably added subsequently in the production of the washing or cleaning agents.

The detergents or cleaning agents can contain customary ingredients such as anionic, nonionic, cationic, zwitterionic and / or amphoteric surfactants in customary amounts, preferably between 5 and 40% by weight, inorganic water-soluble builder substances, for example phosphates, crystalline sheet silicates, amorphous silicates and / or alkali carbo- nat, but also inorganic water-insoluble builder substances, for example zeolite A, P and / or X, further organic builder substances, in particular (co) polymeric salts of acrylic acid and / or maleic acid, bleaching agents, preferably perborate and / or percarbonate, bleach activators and / or bleaching catalysts as described above, graying inhibitors, phosphonates, dye transfer inhibitors and / or ingredients which prevent the dirt from being re-absorbed, enzymes, in particular proteases, amylases, lipases, cellulases and / or (per) oxidases, foam inhibitors and, if appropriate contain neutral salts such as alkali metal sulfates.

Particularly preferred detergents or cleaning agents contain the powdery to granular additive in amounts of 3 to 10% by weight, the additives particularly containing those which are free from bleach activators and / or bleach catalysts.

In a further advantageous embodiment, the detergents or cleaning agents contain an additive as an admixture component, which has bicarbonate, organic polycarboxylic acids and binders in amounts of 80 to 100% by weight and surfactants in amounts of 0 to 5% by weight, a surfactant-free one Additive is clearly preferred. The additive may very well contain fragrances in amounts of 2 to 10% by weight and / or dyes in less than 1% by weight.

Examples

Additives A, B and C of the composition given below were prepared. The solids were placed in a Lödige mixer and perfume and the binder were added in molten form in the usual way. The dye in A and B was previously mixed into the binder melt.

Composition in% by weight:

A B C

Sodium bicarbonate 49.1 34.47 50.0

Citric acid (1 mole water) 35.6 25.0 40.0

Polyethylene glycol (relative molecule 10.0 7.0 10.0 mass 4000)

Tetraacetylethylenediamine - 29.8 -

Dye (dissolved in PEG 4000) 0.0035 0.0035 -

Perfume 5.3 3.73 -

The dissolving behavior of the additives was measured using a residue test: 8 g of the additive to be tested were sprinkled into a 2 l beaker while stirring (800 rpm with a laboratory stirrer / propeller stirring head centered 1.5 cm from the beaker bottom). The test was carried out at 16 ° d. The wash liquor was then poured off through a sieve. The beaker was rinsed over the sieve with very little cold water. A double determination was carried out. The sieves were dried to constant weight in a drying cabinet at 40 ° C ± 2 ° C and the residue was weighed out. The residue is reported as the average of the two individual ^{determinations'} in percent. If the individual results deviate from each other by more than 20%, further tests are carried out.

The deviations for A, B and C were significantly below 20%, so that no further tests had to be carried out. The residues after 1.5 minutes were 0% for additive A, 17% for B and 0% for C.

Claims

claims 1. Use of a powdery to granular additive for use in detergents or cleaning agents for water softening of the washing or cleaning liquor and at the same time promoting foam formation in the liquor, containing bicarbonate and organic polycarboxylic acids, in addition a raw material or compound which or at a pressure of 1 bar and temperatures below 45 ° C is in solid form, but is present as a melt under the processing conditions, this melt serving as a water-soluble binder is included, with the proviso that the bicarbonate, organic polycarboxylic acid content of the additives and binder is at least 60% by weight and the additive contains surfactants in amounts from 0 to below 5% by weight. 2. Use according to claim 1, characterized in that an additive is used which contains more than 30 wt .-% bicarbonate and 20 to 50 wt .-% polycarboxylic acid. 3. Use according to claim 1 or 2, characterized in that the content of bicarbonate in the additive is always greater than the content of organic polycarboxylic acid. 4. Use according to one of claims 1 to 3, characterized in that polyethylene glycols with a relative molecular weight of up to 12,000, in particular with a relative molecular weight of 4,000 or 6,000, are used as binders. 5. Use according to one of claims 1 to 4, characterized in that an additive is used which contains 5 to 15 wt .-%, preferably 7 to 12 wt .-% binder. 6. Use according to one of claims 1 to 5, characterized in that the content of bicarbonate, organic polycarboxylic acids and binders in the additive used is above 65% by weight. 7. Use according to one of claims 1 to 6, characterized in that the additive is free of bleach activators and / or bleach catalysts. 8. Use of an additive according to any one of claims 1 to 7 in detergents or cleaning agents in amounts of 3 to 10 wt .-%. 9. Detergent or cleaning agent containing a powdery to granular additive which contains bicarbonate and organic polycarboxylic acids as well as a raw material or a compound which is in solid form at a pressure of 1 bar and temperatures below 45 ° C under the process conditions but is in the form of a melt, this melt serving as a water-soluble binder, with the provisos that the additive content of bicarbonate, organic polycarboxylic acids and binder is at least 60% by weight, the additive surfactants in amounts from 0 to below Contains 5 wt .-% and has a residue (measured after the residue test) of a maximum of 10%. 10. Composition according to claim 9, characterized in that it contains the powdery to granular additive in amounts of 3 to 10 wt .-%. 11. Detergent or cleaning agent according to claim 9 or 10, characterized in that the powdery to granular additive is free of bleach activators and / or bleach catalysts. 12. Composition according to claim 9 to 11, characterized in that it contains an additive which has bicarbonate, organic polycarboxylic acids and binders in amounts of 80 to 100 wt .-% and surfactants in amounts of 0 to 5 wt .-%, wherein a surfactant-free additive is preferred. 13. Composition according to one of claims 9 to 13, characterized in that it contains an additive that consists of 2 to 10 wt .-% of fragrances and / or less than 1 wt .-% of dyes.