WO2008055788A2 - Washing agent or detergent with improved properties - Google Patents

Abstract

The invention relates to a washing agent or detergent or a constituent thereof, comprising at least two different particulate constituents, the first particulate constituent being a spray-dried powder, granulated material and/or an agglomerate, and the second particulate constituent comprising a core and a shell, at least 30 wt. % of the shell consisting of a material corresponding to the first particulate constituent. Said washing agents or detergents enable non-reactive powdering agents which are generally used to improve the flow properties of sticky, particulate constituents to be dispensed with. According to a method for producing such agents, a constituent which is in a pourable and/or sprayable form between 15 and 40°C is applied to a carrier material, forming a particulate but not free-flowing intermediate product, before the intermediate product is mixed with a particulate constituent. The weight ratio of the particulate constituent in relation to the particulate but not free-flowing intermediate product is higher than 1:9.

Description

 "Detergents or cleaning agents with improved properties"

The present invention relates to a washing or cleaning agent or a component thereof, a process for the preparation of this agent or this component, a process for washing or treating textiles or hard surfaces, in which this agent or this component is used, as well as Use of a base component for a washing or cleaning agent for improving the flow properties of a non-free-flowing small component compound prior to use of the base component.

Modern powdery to granular detergents or cleaners are produced today, for example, by mixing and / or granulating raw materials, additives and prefabricated particulate components, it also being possible for some of the additives and raw materials to be present in liquid form at the processing temperature.

The problem often arises during processing that components must be incorporated that are present only to a small percentage in the finished product. If such "small components" are added to the washing or cleaning agent in the form of pure substances, the problem of segregation arises.Also, if the small components to be incorporated are liquid at the processing temperature, another problem is - due to the unfavorable proportions of liquid small component and solid - observed uneven loading of the solids with the liquid minor component, which also leads to an insufficient distribution of the minor component in the washing or cleaning agent and results in a non-constant washing or cleaning performance of the agent In some parts of the medium, supersaturation results, which lead to sticking and lingling of the medium, which inevitably leads to a worsening of the solubility, the trickling behavior, the visual impression and, in turn, the distribution of the individual Components of the detergent or cleaning agent in the agent by itself.

Small components also include nonionic surfactants in many common washing or cleaning agent formulations. If these are compounded together with the usual constituents of a washing or cleaning agent, in particular together with anionic surfactants, in a granulate, these compositions often have poor flowability and a high tendency to form clumps. These poor properties are especially observed when the granules a high anionic surfactant content, for example more than 10% by weight of anionic surfactant, and a high nonionic surfactant content, for example more than 4% by weight of nonionic surfactant. To circumvent these disadvantages, it is often considered to use the nonionic surfactant as a separate component of a washing or cleaning agent.

The spraying of the liquid component nonionic surfactant onto a particulate component, for example a particulate base component of a washing or cleaning agent, is, like other liquid small components, subject to the disadvantages already described above.

One way around the problems mentioned, is to assemble the liquid small components within a particulate small component compound and then mix this with the other ingredients of the detergent or cleaning agent. These particulate small component compounds often comprise a carrier material to which the liquid minor component is applied. The resulting, in most cases, sticky intermediate is then provided with a powdered powder coating which is intended to improve the flowability of the small component compound. As a powder, for example, zeolites, carbonates, sulfates or silica are used. The known Abwuderungsmittel usually have a mean particle diameter below 50 microns and often are components that, while serving the powdering of the Kleinkomponentencompound, but - apart from any builder properties - have no detergents or cleaning agents specific reactivity.

It is an object of the present invention to avoid some, if possible, all of the abovementioned disadvantages, and in particular to provide a washing or cleaning agent or a component therefor, which - despite good flowability - requires less non-reactive Abwuderungsmittel than conventional means.

With the present invention, this object is achieved.

The present invention is a detergent or a component thereof, comprising at least two different particulate components, wherein a) the first particulate component P is a spray-dried powder, a granule or an agglomerate and b) the second particulate component R is a core K and a shell S, wherein the shell S consists of at least 30 wt .-% of a material corresponding to the first particulate component P. The agent according to the invention preferably contains the first particulate component P and the second particulate component R in a weight ratio greater than 1: 5, preferably greater than 1: 4, more preferably greater than 1: 3, even greater than 1: 2 and more preferably greater than 1: 1 ,

Like the second particulate component R, the first particulate component P can also comprise particles which have a core-shell structure. Particularly preferably, the first particulate component P is a base component for a washing or cleaning agent. In the context of the present invention, basic components for detergents or cleaners are understood as meaning pulverulent, granular or agglomerate-like components which contain a plurality of constituents of the washing or cleaning agent. Preferably, a base component of a washing or cleaning agent contains at least 3, preferably at least 4 and in particular at least 5 different detergent or cleaning agent components. Builders, surfactants, especially anionic surfactants, polymers, bleaches, bleach activators, bleach catalysts, corrosion inhibitors, electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, antiredeposition agents, soil repellent substances, optical brighteners are particularly preferred in the base component , Graying inhibitors, anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, repellents or impregnating agents, swelling or anti-slipping agents and / or UV absorbers. Geeigente representatives of these groups will be mentioned later in the text.

The anionic surfactant content of the first particulate component P is preferably between 0.25 and 45% by weight, preferably between 0.5 and 40% by weight, more preferably between 1 and 35% by weight and in particular between 2 and 30% by weight. %, based on the first particulate component P. In a particularly preferred embodiment, the first particulate component P contains from 15 to 30% by weight of anionic surfactant.

As the first particulate component P, the composition according to the invention preferably contains a spray-dried powder. This usually includes the non-temperature sensitive components of a detergent formulation. In addition to the first particulate component P and the second particulate component R, the composition according to the invention may comprise further components, for example enzyme, bleaching agent, perfume or else optical brightener in particulate and / or liquid form.

The second particulate component R necessarily has a core-shell structure. Essential to the invention consist at least 30 wt .-% of the shell S of the second particulate component R from a material corresponding to the first particulate component P. The second particulate component R can be prepared, for example, by the core K the second component R with a material corresponding to the first particulate component P, which is optionally present in admixture with one or more further particulate component ^) is powdered. Details of suitable methods of preparation of the agent according to the invention will be described later in the text.

Depending on the proportion by weight of the material corresponding to the first particulate component P in the particle mixture with which the core K is powdered, the proportion of the material corresponding to the first particulate component P in the shell S of the second particulate component R varies Preferably, the shell S of the second particulate component R to at least 35 wt .-%, preferably at least 40 wt .-%, more preferably at least 45 wt .-%, with particular preference to at least 50 wt .-% and in particular to at least 55 wt .-% of a material corresponding to the first particulate component P. In special cases, the proportion of the material corresponding to the first particulate component P in the shell S of the second particulate component R at least 60 wt .-%, preferably at least 65 % By weight, more preferably at least 70% by weight, even more preferably at least 75% by weight, most preferably gt at least 80 wt .-%, even more preferably at least 85 wt .-%, more preferably at least 90 wt .-% and in particular at least 95 wt .-% amount. In addition to a material corresponding to the first particulate component P, the shell S of the second particulate component R may comprise further, preferably finely divided, powders, agglomerates and / or granules. Preferably, in the shell S in addition to the first particulate component enzyme, bleach, perfume preparations (granules) or optical brightener and mixtures of these components in particulate form. The shell S of the second component R may also contain known to those skilled powdering agents such as zeolites, silicates, carbonates or silica, which are not part of a particulate component comprising two or more constituents. The shell S of the second particulate component R may contain, for example, zeolites as a constituent of a spray-dried base powder of a washing or cleaning agent. However, it is preferred that powdering agents which are not part of a particulate component comprising two or more constituents, for example those which are not constituents of a spray-dried base powder, be less than 45% by weight, more preferably less than 35% by weight. , are preferably less than 25 wt .-%, more preferably less than 15 wt .-% and in particular less than 5 wt .-% in the shell S, wherein the information on the shell S of the second particulate component R as well as the sum of the contained powdering agents are based.

The core K of the second particulate component R is particularly preferably a small component compound. In the context of the present invention, the term "small component compound" is taken to mean particulate components which contain such substances which are contained in the final formulation of the washing or cleaning agent in low percentages, for example in amounts less than 10 wt .-%, preferably less than 5 wt .-%, based on the final formulation of the agent. Usually, the concentration of the minor component in a small component compound is well above the concentration of the same minor component in the final formulation of the detergent or cleaning agent. Preferred small components are polymers, cobuilders, optical brighteners, perfume, sequestering agents, grayness inhibitors, soap, enzymes, pH adjusters, dyes, foam inhibitors, antiredeposition agents, dye transfer inhibitors and corrosion inhibitors, which, however, individually may also be present in all conceivable combinations in the small component compound , In the context of the present invention, minor components include nonionic surfactants. In the context of the present invention, nonionic surfactant is also referred to as a small component in compositions which contain more than 10% by weight of nonionic surfactant in the final formulation. The second particulate component R, comprising the core K formed from the small component compound and the shell S, preferably contains 0.5 to 52 wt .-%, preferably 0.75 to 47 wt .-%, particularly preferably 1, 0 to 42 wt % and in particular 1, 0 to 37 wt .-% of one or more small components, wherein the wt .-% - information on the second particulate component R, corresponding to core K plus shell S and the sum of the core in the K and the Shell S contained small components are related. Particularly preferred in the context of the present invention are means in which the core K of the second particulate component R is formed by a highly concentrated small component compound. In these cases, the core K of the second particulate component R preferably contains 7.5 to 55 wt .-%, preferably 10 to 52.5 wt .-% and particularly preferably 12.5 to 50 wt .-% of one or more small components , where the wt .-% - information is based on the mass of the core and the sum of the weight fractions of all contained in the core small components.

In a preferred embodiment of the composition according to the invention, the core K of the second particulate component R is formed from a nonionic surfactant compound which contains 9 to 40% by weight, more preferably 10 to 35% by weight and especially 1 to 30% by weight. Nonionic surfactant, based in each case on the core K and the sum of all nonionic surfactants contained in the core.

The preferred subject matter of the present invention is a washing or cleaning agent or a component therefor comprising at least two different particulate components, wherein a) the first particulate component P is a spray-dried powder, in particular a base powder of a washing or cleaning agent comprising 15 to 30% by weight. % Anionic surfactant, and b) the second particulate component R comprises a core K containing 9 to 40 wt .-%, in particular 10 to 35 wt .-% of nonionic surfactant, and a shell, wherein the shell S to at least at least 30 wt .-%, preferably at least 35 wt .-% and in particular at least 40 wt .-% of a material corresponding to the first particulate component P, wherein the weight ratio between the first particulate component P and the second particulate component R greater than 1: 5, preferably greater than 1: 4, more preferably greater than 1: 3 and in particular greater than 1: 2.

It has been found that the present invention has additional advantages when the core of the second particulate component R contains a small component compound comprising a minor component which is in flowable and / or sprayable form at the processing temperature. With preference the core K of the second particulate component R comprises a component F, which is present in the range of 15 to 4O ⁰ C in flowable and / or sprayable form, and is preferably selected from surfactants, especially nonionic and / or anionic surfactants, polymers, Perfume oils, defoamer substances and / or mixtures of these components.

In these embodiments of the present invention, the core K of the second particulate component R can be formed by a small component compound which has an exceptionally high concentration of a free-flowing and / or sprayable small component F without the flowability or clumping properties of the inventive composition comprising the first particulate component P and the second particulate component R are adversely affected by the high content of the flowable and / or sprayable small component F in the core K of the second particulate component R. Preferably, the core K of the second particulate component R comprises 7.5 to 55 wt .-%, preferably 10 to 52.5 wt .-% and particularly preferably 12.5 to 50 wt .-% of the component F, in which case the wt .-% - are based on the mass of the core K and the sum of the weight fractions of all contained in the core components F. The property of flow and / or sprayability of the component F in a range of 15 to 40 ⁰ C refers to a pressure of 1 bar.

In the case of small-component compounds which, for example, have a high tackiness and thus only a low or no flowability due to the high concentration of flowable and / or sprayable components, the advantages of the present invention are particularly evident. To set an acceptable flowability and acceptable clumping properties, sticky compounds must be coated with significant amounts of powdering agent. If now, as described in the prior art, non-reactive Abwuderungsmittel used, the final formulation will contain the reactive detergent or cleaner ingredients in lower concentration, as an inventive means in which the coating of the sticky compound no or less non-reactive Abwuderungsmittel, but for example the base powder a detergent was used. Compared with agents which have a comparable composition but additionally non-reactive Abwuderungsmittel or contain more non-reactive Abwuderungsmittel than inventive compositions, the inventive compositions have a higher washing or cleaning activity.

Furthermore, in the compositions according to the invention an improvement in the physical properties, in particular the flowability, Klummigenschaften and bulk material resistance in comparison to known compositions in which small components are included observed. An improvement in the physical properties was observed particularly in comparison with those containing small components as defined in component F. The superiority of the agents of the invention in physical properties is evident both in comparison with those of the prior art in which the minor components are a constituent of a basic component, for example a spray-dried base powder of a detergent or cleaner, as well as in comparison with such known agents, in which the small components within a small component compound are mixed with the other particulate components of an agent.

A particularly preferred embodiment of the agent according to the invention is the core K of the second particulate component R is a Niotensidcompound dar. Here, it is particularly preferred if the or at least a portion of the nonionic surfactant contained in the core K in the range of 15 to 4O ⁰ C in flow - and / or sprayable form is present. Accordingly, it is of particular advantage if the component F in the core K of the second particulate component R comprises a nonionic surfactant or a mixture of at least two, preferably two to four nonionic surfactants, preferably at least one of the nonionic surfactants to a alkoxylated compound.

All non-ionic surfactants known to the person skilled in the art may be used as a small component nonionic surfactant ("nonionic surfactant" in the context of these examples). [Schwach besonder] Low-foaming nonionic surfactants are used as preferred surfactants, detergents or cleaning agents containing nonionic surfactants from the group of alkoxylated ones As nonionic surfactants it is preferred to use alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably methyl-branched in the 2-position However, in particular, alcohol ethoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, eg from coconut, palm, tallow fat, are present in the mixture or may contain linear and methyl-branched radicals in the mixture. od he oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol. Among the preferred ethoxylated alcohols include For example, C- | ₂ - ₁₄ -alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, Ci ₃ .i ₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C- | ₂ - ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C- | ₂ - ₁₄ -alcohol with 3 EO and C- | ₂ - ₁₈ -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). Alternatively or in addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.

Another class of preferred nonionic surfactants 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 having from 1 to 4 carbon atoms in the alkyl chain.

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

Further suitable surfactants are polyhydroxy fatty acid amides of the formula

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

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

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 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, where Ci_ ₄ alkyl or phenyl radicals are preferred and [Z] is 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 be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

With particular preference, combinations of one or more tallow fatty alcohols containing 20 to 30 EO and silicone defoamers are furthermore used.

Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO / AO / EO nonionic surfactants, or the PO / AO / PO nonionic surfactants, especially the PO / EO / PO nonionic surfactants are particularly preferred. Such PO / EO / PO nonionic surfactants are characterized by good foam control.

Further preferred small components in the invention are polymers, cobuilders, optical brighteners, perfume, sequestering agents, grayness inhibitors, soap, enzymes, pH adjusters, dyes, foam inhibitors, anti redeposition agents, dye transfer inhibitors and corrosion inhibitors. However, the individual components can also be contained individually in all conceivable combinations with one another in the small component compound, which preferably forms the core K of the second particulate component R. The group of polymers includes, in particular, the washing or cleaning-active polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

"Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate , the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may, for example, be carboxylic acids, sulfonic acids or phosphonic acids.

As perfume oils or perfumes, within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable support materials in this case, for example, inorganic salts such as carbonates or sulfates, cellulose losederivate or silicates and mixtures of the aforementioned materials. In the context of the present application preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R ₂ SiO) _x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000 and viscosities between 10 and 1,000,000 mPa.s. Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and phosphonates. Useful are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder effect, the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Also suitable are polymeric polycarboxylates, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights indicated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were fundamentally determined 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 polymers investigated.

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 of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again 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 from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing as monomers, salts of acrylic acid and the Maleic acid and vinyl alcohol or vinyl alcohol derivatives or containing as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate or acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which have at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups contain.

Optical brighteners (so-called "whiteners") may be added to laundry detergents or cleaners to remove graying and yellowing of the treated fabrics which will attract the fiber and cause lightening and fake bleaching by exposing invisible ultraviolet radiation to visible, longer wavelength light convert the absorbed from sunlight ultraviolet light is radiated as a pale blue fluorescence and the yellow shade of the grayed or yellowed laundry to yield pure white Suitable compounds originate for example from the substance classes of the 4,4 ^{'diamino-2,2'.} - stilbenedisulfonic (flavonic), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, and pyrene derivatives substituted by heterocycles.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful. Also usable as graying inhibitors are cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.

Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.

In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited.

When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light as well as not too high an affinity for textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies.

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofarads.

As a small component suitable enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus lichenifor- mis, from β. amyloliquefaciens, from β. stearothermophilus, from Aspergillus niger and A. oryzae, as well as the further developments of the invention which have been improved for use in detergents and cleaners aforementioned amylases. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from β. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectins), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Particular preference is given to using perhydrolases in the compositions according to the invention.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferable to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the electron flow at greatly varying redox potentials between the oxidizing enzymes and the soils (mediators). ,

Of the known sequestering agents, especially the salts of polyphosphonic acids and in particular the neutral reacting sodium salts of, for example, 1-hydroxyethane-1, 1-diphosphonate (HEDP), diethylenetriaminepenta-methylenephosphonate and / or ethylenediaminetetra methylenephosphonate are preferred. The use of nitrilotriacetic acid and / or its salts (NTA) may possibly be less conceivable from an ecological point of view. Likewise, the use of ethylenediaminetetraacetic acid and / or salts thereof (EDTA) would be conceivable from the principle of the invention. However, the use of EDTA is omitted for the known reasons. Color transfer inhibitors are intended to prevent the washing of colored textiles that peeled dye rears on other textiles and stains them. Suitable substances come from the group of polymers, with polyvinylpyrrolidone occupying an outstanding position.

The core K of the second particulate component may contain further constituents which are solid and / or flowable in the processing and / or storage conditions. Particularly in those cases in which the core contains a component F, the sprayable form is present in the range of 15 to 4O ⁰ C in flowable and / or the core K comprises with advantage at least one solid, in particular a support material T.

Preferably, the core K contains an inorganic carrier material, in particular inorganic salts. Organic support materials are in the core K of the second particulate component R preferably in amounts less than 25 wt .-%, more preferably less than 15 wt .-% and in particular less than 5 wt .-%, based on the core K and the sum of all in the core K present carrier materials. In the context of the present invention, it is preferred that the core K of the second particulate component R comprises a support material T which comprises carbonates, bicarbonates, sesquicarbonates, sulfates, silicates, aluminosilicates, silicic acids, citric acid, citrates and / or tripolyphosphates.

The carrier material preferably has an oil absorption capacity of from 10 ml / 100 g to 160 ml / 100 g, preferably from 12.5 ml / 100 g to 120 ml / 100 g and especially from 15 ml / 100 g to 80 ml / 100 g. Oil absorption capacity is a physical property of a substance that can be determined by standardized methods. The oil absorption capacity for the purpose of this application is determined by means of the method defined in the international standard ISO 787/5. This is done by placing a well-balanced sample of the substance on a plate and dropwise adding to it a refined burl of refined linseed oil (density: 0,93 ^"3 ) .After each addition the powder is mixed intensively with the oil using a spatula This paste should flow without crumbling, the oil absorption capacity is now the amount of oil dropped relative to 100g of absorbent and is expressed in ml / 100g or g / l. 100g, where conversions about the density of linseed oil are easily possible.

Is used as component F which is present in the range of 15 to 4O ⁰ C in flowable and / or sprayable form, nonionic surfactant, the ratio between the nonionic surfactant is (component F) and base material T in the core K of the second particulate component R preferably at 10 ml of nonionic surfactant / 100 g of carrier material to 40 ml of nonionic surfactant / 100 g of carrier material and in particular 20 ml of nonionic surfactant / 100 g of carrier material to 30 ml of nonionic surfactant / 100 g of carrier material. The preferred subject matter of the present invention is a washing or cleaning agent or a component thereof comprising at least two different particulate components, wherein, a) the first particulate component is a spray-dried powder, a granulate or an agglomerate, in particular a spray-dried base powder of a washing or cleaning agent is, which preferably comprises 15 to 30 wt .-% anionic surfactant, and b) the second particulate component R comprises a core K and a shell S, wherein the shell S to at least 30 wt .-% of a material corresponding to the first particulate Component P, and wherein the core K contains a carrier material which preferably comprises carbonates, hydrogencarbonates, sesquicarbonates, sulfates, silicates, aluminosilicates, silicic acids, citric acid, citrates and / or tripolyphosphates, the core K one or more in the range from 15 to 40 ⁰ C in sprayable flowable and / or shape vorli niotenside (s), in particular ethoxylated nonionic surfactant (s), wherein the ratio between nonionic surfactant and carrier material in the core K is 10 ml of nonionic surfactant / 100 g of carrier material to 40 ml of nonionic surfactant / 100 carrier material Information on the core K, the sum of the carrier materials contained in the core K and the sum of the contained in the core K, in the range of 15 to 40 ⁰ C present in flowable and / or sprayable form nonionic surfactants are present, and the weight ratio between the first particulate component P and the second particulate component R is greater than 1: 5.

Further washing or cleaning agent ingredients which may be a constituent of the first particulate component P and / or optionally present additional particulate or liquid components in the compositions according to the invention are listed below. These components may also be part of the second particulate component, for example, part of the carrier material T in the core K or the shell S. Likewise, the small components already mentioned above can also be part of the first particulate component P.

The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates. Suitable cobuilders have already been mentioned.

The finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and / or P. The zeolite P, zeolite MAP ^® (Crosfield commercial product) is most preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and preferably used in the context of the present invention. bar is, for example, a co-crystallizate of zeolite X and zeolite A (about 80 wt .-% zeolite X), represented by the formula

n Na ₂ O ^■ (1-n) K ₂ O ^■ Al ₂ O ₃ ^■ (2 - 2.5) SiO ₂ ^■ (3.5-5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular compound and for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, whereby usually both ways of incorporating the zeolite into the premix are used an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

With preferred crystalline layered silicates of general formula NaMSi _x O are used _{2x + 1} ^■ y H ₂ O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O are sold for example by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ ^.xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ ^.xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ ^.xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ ^.xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline layer silicates with the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O, in which x stands for 2 h. In particular, both .beta.- and δ-Na triumdisilikate Na ₂ Si ₂ O ₅ ^■ y H ₂ O, and further in particular Na-SKS-5 (Oc-Na ₂ Si ₂ O _5), Na-SKS-7 (.beta. - Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ^■ H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ ^■ 3 H ₂ O, kanemite), Na SKS 11 (t-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (5-Na ₂ Si ₂ O ₅ ) is preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 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 preferably delayed release and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compacting / compacting or by overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not yield any sharp X-ray reflections in X-ray diffraction experiments, as are typical for crystalline substances, but at most one or more maxima of the scatter X-rays having a width of several degrees of diffraction angle.

Alternatively or in combination with the abovementioned amorphous sodium silicates, X-ray amorphous silicates are used whose silicate particles produce fuzzy or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tri-phosphates are also preferably used according to the invention.

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention. Particularly preferred may be a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Due to their low chemical compatibility with the rest compared to other builders Ingredients of detergents or cleaners, the alkali metal hydroxides are preferably used only in small amounts.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as builders.

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants. Nonionic surfactants (nonionic surfactants) have already been mentioned.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Suitable surfactants of the sulfonate type are preferably C _9-13 alkylbenzene sulfonates, olefinsulfonates finsulfonate, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C _{12-i 8} monoolefins with an internal or terminal double bond by Sui - Fung with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained, into consideration. Also suitable are alkanesulfonates, from C ₁₂ - ₁₈ are obtained -Alka- nen for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization. Likewise suitable are the esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerines are to be understood as meaning the mono-, di- and triesters and mixtures thereof, such as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained. Preferred sulfated 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.

Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester C ₂ -C ₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl ristyl-, cetyl or stearyl alcohol, or d ₀ -C ₂ o-oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of the above-mentioned chain length, which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis, which have an analogous decomposition behavior to the adequate compounds based on oleochemical raw materials. From the washing are the C ₁₂ - C ₆ alkyl sulfates and C ₂ -C ₅ alkyl sulfates and C-ι ₄ -C preferably ₅ alkyl sulfates. The 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants. Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂ i-alcohols, such as 2-methyl-branched Cg-n-alcohols with an average of 3.5 moles of ethylene oxide (EO) or C- | ₂ - ₁₈ -fatty alcohols with 1 to 4 EO are suitable.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -i ₈ -fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are in particular soaps, which may also be small components in the sense of the present invention, into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

Compositions according to the invention preferably comprise more than 10% by weight of anionic and 3 to 10% by weight, in particular 4 to 8% by weight, of nonionic surfactants. Preferably, the agent according to the invention contains alkylbenzenesulfonates.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

As cationic active substances, for example, cationic compounds of the following formulas can be used: R1

Ri-N- (CH _{2) n} -T-R 2 (CH _{2) n} -T-R2

wherein each group R ^{1 is} independently selected from C-. ₆ alkyl, alkenyl or hydroxyalkyl groups; each R ² group is independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer "avivage" and reduced electrostatic charging (increased wear comfort) The active ingredients of these formulations are quaternary ammonium compounds with two hydrophobic radicals, such as, for example, the disterylaldimethyl - Lammoniumchlorid, which, however, due to its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.

Such esterquats having improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se.

The bleaching agents are a particularly preferred washing or cleaning substance. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further useful bleaching agents are, for example, peroxypyrophosphates, Citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxyacids, examples of which include the alkylpolyacids and the aryl peroxyacids.

As a bleaching agent and chlorine or bromine releasing substances can be used. Examples of suitable chlorine or bromine-releasing materials are heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Bleach activators are used in detergents or cleaners, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 ⁰ C and below. As bleach activators, it is possible to use 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 stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2, 5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium acetonitrile-methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylca- pr olactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula R1

R2-N- (CH ₂₎ -cnx ^"

R3

in which R ¹ is -H, -CH _3, a C ₂ - ₂₄ alkyl or alkenyl group, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or Alkenylarylrest with a C |. ₂₄ alkyl group, or for a substituted alkyl or al kenylarylrest with a C |. ₂₄ alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ - CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, - CH ₂ - CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion, preferably from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate. is.

Particular preference is given to compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , (CH ₃ CH (CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X, wherein from the group of these substances turn the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , in which X ^{" is} an anion selected from the group chloride, bromide, iodide, hydrogen sulfate , Methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is particularly preferred.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt ( Amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts. In special cases, however, more bleach activator can also be used.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligands with the donor groups. functionally N, NR, PR, O and / or S included. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Examples of suitable manganese complexes are [Mn ^MI 2 (μ-O) ₁ (μ-OAc) 2 (TACN) 2] (CIO ₄ ) 2, [Mn '"Mn' ^v (μ-O) ₂ (μ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) Z, [Mn ^IV 4 (μ-O) ₆ (TACN) 4] (Clθ4) 4, [Mn ^I " ₂ (μ-O) ₁ (μ-OAc) 2 (Me -TACN) 2] (Clθ4) 2, [Mn ^l "Mn ^lv (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) 3, [Mn ' ^v ₂ (μ-O ) ₃ (Me-TACN) _2] (PF _{6) 2} and [Mn ^'v ₂ (μ- O) ₍₃ (Me / Me-TACN) _2] PF _{6) 2} (OAc = OC (O) CH ₃₎ ,

As electrolyte ^ from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the washing or cleaning agents is preferred.

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and crushing transversely to the fiber direction, synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability. Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents may also be included. The antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. A further field of application of repellents and impregnating agents is the water-repellent finish of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing). The water repellents used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxanes. Groups. Suitable water repellents are, for example, paraffins, waxes, metal soaps, etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, tin-organic compounds and glutaric dialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening. For example, silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.

Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol-mercury acetate, although it is entirely possible to do without these compounds.

To prevent undesirable changes to the detergents and cleaners and / or the treated fabrics caused by exposure to oxygen and other oxidative processes, the compositions may contain anti-oxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased comfort may result from the additional use of antistatic agents. Antistatics increase the surface conductivity and thus enable an improved outflow of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzy- lammoniumchloride are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional Avivageeffekt is achieved.

Silicone derivatives can be used to improve the water absorbency, rewettability of the treated fabrics, and ease of ironing the treated fabrics. These additionally improve the rinsing out of detergents or cleaning agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or Si-OH- , Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and the polyalkylene oxide-modified dimethylpolysiloxanes.

Finally, according to the invention, it is also possible to use UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous urocanic acid.

Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents and cleaners. Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). According to the invention, protein hydrolysates of both vegetable and animal origin can be used. Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Preferred according to the invention is the use of protein hydrolysates of plant origin, e.g. Soy, almonds, rice, pea, potato and wheat protein hydrolysates. Although the use of the protein hydrolysates is preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.

The compositions of the invention are characterized by a good flowability and a low tendency to lump. If detergents according to the invention are metered into the metering drawer of an automatic washing machine, substantially less or no residues are found in the metering chamber after flushing than in the case of conventional means, since there is virtually no or no gelation of the agent according to the invention. Furthermore, there are significantly fewer to no residues on fabrics treated with detergents according to the invention than after treatment with conventional agents, which can be attributed to a very good solubility of the compositions according to the invention.

The compositions according to the invention preferably have a flowability greater than 55%, with preference greater than 60% and in particular greater than 65%. In the clod test, the test results for the compositions according to the invention are preferably at a maximum of 100 g, more preferably at maximum 90 g, more preferably at a maximum of 80 g, in particular at 70 g. The measurement methods for determining the flowability and the lumpiness are given in the examples.

The compositions according to the invention are characterized by good flow behavior, which is of great importance for example for the transport and storage of the agents (storage stability, tack in silos, bunkers and the like). A common standard method for the quantitative determination of the flow behavior of a powder / agglomerate / granules is the determination of the shear stress of a preconsolidated powder. In this method, the sample to be tested is solidified by the application of a certain pressure (solidification stress) and then subjected to the solidified cylindrical bulk material sample a vertical compressive stress which acts on the sample at a defined angle (shear angle). At a certain tension, the sample breaks, that is, to flow. This compressive stress is also referred to as compressive strength or bulk material strength. Thus, there is a bulk-specific flow limit that must be reached in order to make the bulk material to flow. The lower the stress under which the bulk material flows, the better its flowability is to be judged.

The bulk material strength of the compositions according to the invention after solidification at 15000 Pa is preferably between 500 and 4000 Pa, more preferably between 1000 and 3700 Pa and in particular at 2000 to 3500 Pa and / or after solidification at 45000 Pa preferably between 15000 and 20500 Pa, more preferably between 16000 and 20250 Pa and in particular between 18000 and 20,000 Pa. The data apply under the conditions given in the example section for the method for determining the bulk solids strength.

Another object of the present invention is a process for washing or treating textiles or hard surfaces, comprising the step of contacting the textiles or hard surfaces with an aqueous medium containing an effective amount of a detergent or a component according to the invention for this purpose ,

As already described, the second particulate component R can be prepared by contacting the core K of the second component R with a material corresponding to the first particulate component P, which is optionally present in admixture with one or more further particulate component (s) ,

A further subject matter of the present invention is a process for the preparation of a washing or cleaning agent or a component according to the invention for this purpose, comprising the following steps: a) providing a carrier material T, b) loading of the support material T with a component F, which is in the range of 15 to 40 ⁰ C in flowable and / or sprayable form, to form a particulate, but not free-flowing intermediate K and c) loading of the intermediate product K with a particulate Component, wherein the weight ratio of the particulate component used in step c) to the particulate, but not free-flowing intermediate K is greater than 1: 9.

In the preparation of compositions according to the invention, in process step c) not only the amount of a particulate component is used which is needed to spin off the non-free-flowing intermediate K, but a clear excess of this particulate component. Products of the method according to the invention therefore contain, in addition to a particulate component, which has a core which is formed from the non-free-flowing intermediate K and a shell S and should be referred to as the second particulate component R, a further particulate component which consists of the parts of Particulate component is formed, which is used in step c) of the method according to the invention and does not form the shell S to the non-free-flowing intermediate product K. These "residues" of the particulate component used in step c) of the process should be referred to as the first particulate component P.

Preferably, in the process according to the invention, the weight ratio of the particulate component used in process step c) to the intermediate product K, greater than 1: 4, preferably greater than 3: 7, more preferably greater than 2: 3, most preferably greater than 1: 1 and in particular greater than 3: 2. The non-flowing intermediate K corresponds to an inventive composition containing a carrier material T and a component F, which sprayable form is present in the range of 15 to 4O ⁰ C in flowable and / or the core K of the second particulate component R.

In step a) of the process according to the invention, a support material T is preferably provided which comprises carbonates, bicarbonates, sesquicarbonates, sulfates, silicates, aluminosilicates, silicic acids, citric acid, citrates and / or tripolyphosphates. In step b) of the process, preference is given to using a component F which contains surfactants, in particular nonionic and / or anionic surfactants, polymers, perfume oils and / or antifoam substances.

The addition of the particulate component in process step c) improves / ensures the flowability of the intermediate K. Particularly good results in terms of flowability and low lumpiness of the final process product are obtained if the particulate component used in process step c) contains a high proportion of particles which a Particle diameter below 0.2 mm. With special preference in the Step c) of the method uses a particulate component which consists of at least 5 wt .-%, preferably at least 10 wt .-% and in particular at least 15 wt .-% of particles having a particle diameter below 0.2 mm , At the same time, the mean particle diameter d _{50 of the} same particulate component is preferably between 0.2 and 1.4 mm, more preferably between 0.4 and 1.2 mm and in particular between 0.5 and 1.0 mm.

The person skilled in suitable methods for the determination of the particle size and the average particle diameter of powders, granules and agglomerates are well known. In the context of this invention, the particle sizes were determined by sieve analyzes. The term "average particle diameter d ₅₀ " is understood to mean the value at which 50% of the particles have a smaller diameter and 50% of the particles (each based on the number of particles) have a larger diameter.

In a preferred embodiment of the process according to the invention, in step c) of the process a particulate component is used which comprises a spray-dried powder, a granulate or an agglomerate, wherein the powder, granules or agglomerate is particularly preferably a base component of a washing or cleaning agent. What is understood in the context of this invention by the term "base component" has already been carried out in advance.

It should be expressly pointed out that the information on the constituents of the agent according to the invention, such as the properties of the carrier material, the composition of the core K of the second particulate component R or to the nature of the first particulate component P, which in advance in Connection with the agents according to the invention were also valid for the inventive method.

The loading of the carrier material T with the component F and formation of the non-free-flowing intermediate product K and the subsequent metered addition of a particulate component can be carried out in one or more mixers connected in series. Suitable mixers are free-fall mixers, push and throw mixers, gravity mixers and pneumatic mixers. Preferred free-fall mixers are drum, tumble, cone, double cone and V mixers. Shear mixers refer to mixers with moving mixing tools in which the mixing tools move at a low speed. Examples of suitable mixers are screw mixers and spiral belt mixers. High-speed mixers with agitated mixing tools are referred to as litter mixers and include, for example, paddle, ploughshare, paddle and ribbon mixers. As a mixer with moving container and moving mixing tools preferably plate mixer and countercurrent intensive mixer are used. Suitable gravity mixers include mixed silos, bunkers or belts. As a suitable pneumatic mixers are again considered mixed silos, fluidized bed mixers and jet mixers.

If the process according to the invention is carried out in only one mixer, then the particulate component in process step c) is preferably metered in for a maximum of 30 seconds, more preferably 15 seconds and especially 0.1 to 10 seconds after the loading of the carrier material T with the component F. A preferred mixer in this case is a free-fall mixer, which preferably does not contain any movable mixing tools. Suitable free-fall mixers have already been described. However, it is also possible to perform such a preferred method in a mixer having movable mixing tools. Such a mixer, in particular a moderate or high-speed mixer is operated in this case preferably without a knife (fast-running shoppers in the case of a plowshare mixer).

In a preferred embodiment, the method according to the invention is carried out such that the method steps b) and c) are carried out in different mixers. It is particularly preferred if step b) in a moderate or high speed mixer, in particular a Schugi® Flexomix, Pflugschar-, ribbon or pin mixer, for example Lödige® CB, KM or FM mixer, Eirich® mixer, Fukae® Series FS-G mixer, Drais® KT mixer, Henschel® mixer, Diosna® V mixer, Pharma Matrix® mixer, Fuji® mixer VG-C or Roto® mixer.

In process step c), preference is given to using a mixer with low shear, in particular a free-fall mixer. The mixers particularly preferably used in process step c) include drum, tumble, cone, double cone and V mixers as well as belts, bunkers and plate mixers. Particular preference is given to using a double-cone mixer with a rotatable container. Also suitable is a Forberg® mixer.

The component F is preferably sprayed onto the moving carrier material by means of nozzles. The spraying can be carried out by means of single-component or high-pressure spray nozzles, two-component spray nozzles or three-spray nozzles. For spraying with Einstoffsprühdüsen the application of a high melt pressure is required while the spraying takes place in two-component spray nozzles by means of a Preßluftstromes. Spraying with two-component spray nozzles is more favorable, in particular with regard to possible clogging of the nozzle, but is more complicated due to the high compressed air consumption. As a modern development, there is the three-component spray nozzles, which in addition to the Preßluftstrom for atomization another air ducting system to prevent clogging and dripping at the nozzle. Within the scope of the process according to the invention, the use of dual-substance spray nozzles is particularly preferred. Preferably, the component F is sprayed as uniformly as possible on the carrier material T. It has proved to be advantageous if, in the course of Step b) per 100 g of carrier material 10 to 40 ml, in particular 20 to 30 ml of the component F are sprayed.

Particularly preferably, in step b) the carrier material T is applied in a moderate or high-speed mixer with the component F and swirled after being applied for another 0.5 to 15 seconds, especially 1 to 5 seconds, preferably no granulation takes place in step b ) formed particulate, but not free-flowing intermediate K in a free-fall mixer, shear mixer, bunker, pneumatic mixer or transferred to tapes and there acted upon in step c) with the particulate component P and mixed.

The mixers used in the process are preferably controlled such that in step b) and / or in step c) of the process, preferably in both process steps, the respective mixer is operated at a Froude number of at most 2, preferably at most 1. Particularly free-flowing products are obtained if granulation does not take place either in process step b) or in process step c).

In step c) of the process, in addition to the particulate component to be used according to the invention, further particulate and / or liquid components can be introduced into the process. A spray-dried powder which preferably contains at least 3, preferably at least 4 and in particular at least 5 detergent or cleaner constituents, is preferably used in the process as the particulate component to be used according to the invention. In addition to this base powder, further granules and / or agglomerates are preferably metered in process step c). The proportion of free-flowing and / or sprayable components metered in process step c) is preferably below 15% by weight, more preferably below 10% by weight, more preferably below 5% by weight, most preferably below this of 2 wt .-%, in particular below 1 wt .-%, wherein the data are each based on the product of process step c). The granules and / or agglomerates optionally added in process step c) preferably contain those constituents of a detergent or cleaning agent formulation which are sensitive to temperature and are therefore not compounded within a spray-dried powder, or which incompatibilities with detergent or cleaner constituents contained in the base component are, show.

In a particularly preferred embodiment of the process according to the invention, the particulate but not free-flowing intermediate K in process step c) is mixed with a spray-dried base powder of a washing or cleaning agent in a weight ratio of less than 2: 1 and optionally with defoamer, enzyme, bleach, fragrance Components and / or optical blended bright and simultaneously mixed into a finished product. This embodiment is particularly advantageous, since not only a separate component component compound is prepared here, but the particulate, but not free-flowing intermediate product K is simultaneously powdered and mixed with the other solid and optionally liquid components of the final formulation to the final product. Compared to the conventional process management with separate small component compound production, storage and dosage in this process management the Abpuderungseinheit the non-free-flowing intermediate product K, the storage unit of the powdered intermediate (small component compounds) and its delivery unit for final mixing saved. The same advantages arise when the intermediate K is not mixed with other particulate components directly to the final product, but to a "higher intermediate".

Another object of the present invention is the use of a base component for a detergent or cleaning agent which has at least 10 wt .-% has a particle diameter below 0.2 mm, to improve the flow properties of a non-free-flowing prior to use of the base component small component compound. In this case, the base component preferably contains at least 3, preferably at least 4 and in particular at least 5 detergent or cleaner ingredients and comprises between 0.5 and 40 wt .-%, preferably between 1 and 35 wt .-%, particularly preferably between 2 and 30 wt .-% and in particular 15 to 30 wt .-% anionic surfactant.

Examples

First process step:

In a Schugi® Flexomix 400 (3 rows of knives, position 0 °), a mixture of Lutensol AO 5 and Lutensol AO 7 is sprayed onto a mixture of sodium carbonate, sodium bicarbonate and sodium sulfate at a speed of 525 min ^-1 . It forms a particulate, but not free-flowing intermediate. The residence time in the mixer is 1 - 2 seconds.

Second process step:

In a drum mixer, the non-free-flowing intermediate from the first process step is mixed with a spray-dried powder and other components listed in the table within 30 to 60 s.

All data in% by weight

Lutensol AO 5: C ₁₃ H ₅ O (CH ₂ CH ₂ ) O) ₅ H ex BASF Lutensol AO 7: C ₁₃ . ₁₅ O (CH ₂ CH ₂ ) O) ₇ H ex BASF Composition of the spray-dried powder:

All data in% by weight

For Examples 1 to 4, the following properties were determined:

The compositions of the invention contain no non-reactive Abwuderungsmittel.

The clump test of the funds is in the acceptable range. The trickle test and the test for determining the bulk solids yielded significantly improved values compared with known means.

Comparative Example

For comparison, a detergent was prepared by spray-drying an anionic surfactant-containing slurries. In contrast to the examples according to the invention, the nonionic surfactant was not introduced into the final product by the formulation of a nonionic surfactant compound but is part of the slurry / spray-dried powder. Composition of the spray-dried nonionic surfactant-rich powder:

All data in% by weight

The following properties were determined for the spray-dried nonionic surfactant-rich powder:

Although the final formulations of Inventive Example 1 and Comparative Example contain comparable amounts of nonionic surfactant, Inventive Example 1 has better physical properties. The final formulations of Examples 2 to 4 according to the invention contain significantly more nonionic surfactant than the product of the comparative example, but are also superior to the comparative example in a lump test, trickle test and bulk solids strength.

migration test

In order to determine the trickling behavior, in each case 1 liter of the sample to be measured was filled into a powder funnel initially closed at its exit direction and then the flow time of the

Samples measured in comparison to dry sea sand. The drainage time of the dry sea sand after release of the discharge opening (13 seconds) was checked at 100% and the times

Samples are related. Values in the range of 65% and above are considered acceptable. aggregation test

To determine the clumping behavior, 15 ml of the sample to be examined were measured in a 15 ml graduated cylinder and transferred into a stainless steel cylinder, which stood in a glass Petri dish. Then, a stainless steel punch, which exactly fits the diameter of the stainless steel cylinder, was inserted into the cylinder and loaded with a weight so that the sample was loaded with a total of 950 g ± 1 g. Care was taken to ensure that the powder was not compressed by forces other than the weight of the stainless steel punch (+ weight).

After 30 minutes at 2O ⁰ C, the weight was removed, the cylinder is raised and the agent pushed out with the punch.

Formed by the clumping of the particles of a dimensionally stable pressure, the glass shell was placed with the pressure under a weighing pan of a beam balance. A beaker was placed on this weighing pan and the balance was weighed out. Now slowly enough water was poured into the beaker until the pressure was broken by the pressure from above. The required amount of water was balanced.

Rating:

If no agglomerate had formed, the clumping test was given as 0%. If the sample was slightly clumped up to one-third of the volume of the sample, the clumping could be broken by light pressure, the clump test rating was 33%. The 50% value was awarded when half of the sample had clumped, allowing the clumping to break up with light pressure.

When two-thirds of the sample was clumped, the clumping test was rated 67%. In this case, also not clumped particles had to be found.

Formed by the clumping of the particles of a dimensionally stable pressure, the clumping test was rated at 100%. The amount of water needed to crush the pressure under the beam balance is expressed in grams.

Determination of bulk solids

Bulk solids are determined using a Johanson Hang-Up Indicator® (Diamondback Technology INC.) In Scientific Mode (Measurement Program 5, Internal Friction Angle 25 °). The measuring cell used is a cylinder with an inner diameter of 54 mm. The bottom of the measuring cell is formed of a movable bottom punch (diameter 48 mm) and a fixed ring of 3 mm width. The bulk material strength is determined at solidification stresses of 15000 Pa and 45000 Pa. For this purpose, the sample to be examined is introduced into the measuring cell, loaded with the respective solidification stress (15000 Pa or 45000 Pa) in the vertical direction and thus solidified. Subsequently, the bottom punch of the measuring cell is shut down, so that the sample is on the ring in the measuring cell.

The solidified bulk sample is then subjected to increasing vertical compressive stress by means of a punch until the sample breaks, that is, the sample begins to flow. The compressive stress value at which the sample begins to flow is reported in Pascal as the measurement result.

Claims

claims

1. washing or cleaning agent or a component thereof, comprising at least two different particulate components, characterized in that a) the first particulate component P is a spray-dried powder, a granulate or agglomerate and b) the second particulate component R is a core K and a shell S, wherein the shell S consists of at least 30 wt .-% of a material corresponding to the first particulate component P.

2. washing or cleaning agent or a component thereof according to claim 1, characterized in that the first particulate component P and the second particulate component R in a weight ratio greater than 1: 5, preferably greater than 1: 4, more preferably greater than 1: 3, very particularly preferably greater than 1: 2 and in particular greater than 1: 1.

3. washing or cleaning agent or a component thereof according to any one of claims 1 or 2, characterized in that the shell S to at least 35 wt .-%, preferably at least 40 wt .-%, more preferably at least 45 wt .-%, with particular preference to at least 50 wt .-% and in particular at least 55 wt .-% of a material corresponding to the first particulate component P.

4. washing or cleaning agent or a component thereof according to one of claims 1 to

3, characterized in that the first particulate component P is a base component for a washing or cleaning agent.

5. washing or cleaning agent or a component thereof according to one of claims 1 to

4, characterized in that the core K of the second particulate component R is a small component compound.

6. washing or cleaning agent or a component thereof according to any one of claims 1 to

5, characterized in that the core K of the second particulate component R comprises a support material T, which contains carbonates, bicarbonates, sesquicarbonates, sulfates, silicates, aluminosilicates, silicas, citric acid, citrates and / or tripolyphosphates.

7. washing or cleaning agent or a component thereof according to any one of claims 1 to

6, characterized in that the core K of the second particulate component R a Component F comprises, which is present in the range of 15 to 4O ⁰ C in flowable and / or sprayable form, and is preferably selected from surfactants, especially nonionic and / or anionic surfactants, polymers, perfume oils, defoamers and / or mixtures of these components.

8. washing or cleaning agent or a component thereof according to claim 7, characterized in that the component F in the core K of the second particulate component R comprises a nonionic surfactant or a mixture of at least two, preferably two to four nonionic surfactants, wherein it is preferably at least one of the nonionic surfactants is an alkoxylated compound.

9. washing or cleaning agent or a component thereof according to any one of claims 1 to

8, characterized in that the core K comprises 7.5 to 55 wt .-%, preferably 10 to 52.5 wt .-% and particularly preferably 12.5 to 50 wt .-% of the component F, wherein the wt. -% - are based on the mass of the core and the sum of the weight fractions of all contained in the core components F.

10. washing or cleaning agent or a component thereof according to one of claims 1 to

9, characterized in that it comprises more than 10 wt .-% of anionic and 3 to 10 wt .-%, in particular 4 to 8 wt .-% of nonionic surfactants.

11. A process for producing a washing or cleaning agent or a component thereof according to any one of claims 1 to 10, comprising the following steps: a) providing a carrier material T, b) loading the carrier material T with a component F, which in the range of 15 to 4O ⁰ C is in flowable and / or sprayable form, to form a particulate, but not free-flowing intermediate K and c) loading of the intermediate K with a particulate component, wherein the weight ratio of the particulate component used in step c) to the particulate, however non-free-flowing intermediate K is greater than 1: 9.

12. The method according to claim 11, characterized in that the weight ratio of the particulate component used in step c) to the intermediate K, greater than 1: 4, preferably greater than 3: 7, more preferably greater than 2: 3, most preferably greater than 1: 1 and especially greater than 3: 2.

13. The method according to any one of claims 11 or 12, characterized in that in step a) of the method, a carrier material T is provided, which carbonates, bicarbonate te, sesquicarbonates, sulfates, silicates, aluminosilicates, silicic acids, citric acid, citrates and / or tripolyphosphates and in step b) of the process a component F is used which surfactants, especially nonionic and / or anionic surfactants, polymers, perfume oils and / or Defoamer substances comprises.

14. The method according to any one of claims 11 to 13, characterized in that in step c) of the method, a particulate component is used which at least 5 wt .-%, preferably at least 10 wt .-% and in particular at least 15 wt .-% consists of particles having a particle diameter below 0.2 mm.

15. The method according to any one of claims 11 to 14, characterized in that in step c) of the method, a particulate component is used, which comprises a spray-dried powder, granules and / or agglomerate, wherein the powder, granules and / or agglomerate particularly preferably represents a basic component of a washing or cleaning agent.

16. The method according to any one of claims 11 to 15, characterized in that in step b) the carrier material T is acted upon in a moderate or high-speed mixer with the component F and after the application of another 0.5 to 15

Seconds, in particular 1 to 5 seconds is vortexed, preferably no

Granulation takes place, the formed in step b) particulate, but not free-flowing intermediate K is transferred to a free-fall mixer, shear mixer, bunker, pneumatic mixer or on belts and there in step c) is acted upon and mixed with the particulate component P.

17. The method according to any one of claims 11 to 16, characterized in that in step b) and / or in step c) of the method, preferably in both method steps, the respective mixer at a Froude number of a maximum of 2, preferably of at most 1 is operated.

18. The method according to any one of claims 11 to 17, characterized in that the particulate, but not free-flowing intermediate K in process step c) with a spray-dried base powder of a detergent or cleaner in a weight ratio less than 2: 1 and optionally with defoamer, enzyme , Bleaching, fragrance components and / or optical brighteners is mixed and simultaneously mixed into a finished product.

19. A process for washing or treating textiles or hard surfaces, comprising the step of contacting the textiles or hard surfaces with an aqueous medium containing an effective amount of a detergent or a component therefor according to any one of claims 1 to 10.

20. Use of a base component for a washing or cleaning agent which has a particle diameter of at least 10 wt .-% below 0.2 mm, to improve the flow properties of a non-free-flowing prior to use of the base component Kleinkomponentencompound.