EP1416040A1 - Water soluble builders with a specific particle size for use in detergents and cleaning agents - Google Patents

Abstract

A detergent or washing agent contains a water-soluble builder of particle size distribution such that particles of sizes from 0.2 to below 0.4 mm are excluded.

Description

The present invention relates to a washing or cleaning agent which contains a water-soluble builder, the builder of a particular one Has grain size distribution, with grain sizes from 0.2 mm to below 0.4 mm are excluded.

Builders or cobuilder systems belong to the most important substance classes for the construction of detergents or cleaning agents. You meet in the Detergents or cleaning agents perform various tasks, among others the water softening, the strengthening of the washing effect, a Graying inhibition and dirt dispersion are. Furthermore the builders are to the alkalinity necessary for the washing process contribute to a high absorption capacity for surfactants and / or others Detergent additives show, improve the effectiveness of surfactants, they can also contribute to positive properties of Deliver solid products in powder form, for example structure formation and control of the dust problem. In some cases, the different requirements with only one builder component alone not meet, so in these cases on a system of builders and Cobuilder is used.

Former water-soluble builders based on phosphorus and / or Nitrogen has come under fire for ecological reasons, whereupon a change to three-dimensionally networked, water-insoluble Builders, e.g. B. zeolites. For water-insoluble builders however, the phenomenon of undesirable occurs to an increased extent Incrustation that required the use of cobuilders. For example, polymers are often used together with zeolites Polycarboxylates, in particular copolymers based on (meth) acrylic acid and maleic acid used together with soda. They are also common Complexing agent used.

Simultaneously with the development of the zeolite NaA as a builder proposed selected water-soluble amorphous sodium silicate compounds as builder substances in washing or cleaning agents use. For example, US Pat. Nos. 3,912,649, 3,956,467, 3,838,193 and 3,879,527. Here are amorphous Sodium silicate compounds described as builder substances by Spray drying aqueous water glass solutions, then grinding and Compacting with additional dehydration of the ground material become.

EP-A-0 444 415 describes a detergent with 0.5 to 60% by weight a builder, 5 to 50% by weight of a surfactant and others usual washing aids, the builder being an amorphous low-water sodium disilicate with a water content of 0.3 to 6% by weight represents. The production of these highly dehydrated amorphous disilicates takes place in a multi-stage process, which initially involves the production of a powdered amorphous sodium silicate with a water content of 15 provides up to 23 wt .-%. This material is used in a rotary kiln Flue gas treated at temperatures from 250 to 500 ° C. That from the Sodium disilicate emerging from the rotary kiln is removed using a mechanical crusher crushed to grain sizes of 0.1 to 12 mm and then grind to grain sizes from 2 to 400 µm.

Patent applications WO 96/20269 and WO 97/34977 both describe amorphous alkali silicates containing ingredients of washing or Detergents, especially ingredients (e.g. Surfactants) in liquid form. In both applications, the Applying and granulating the silicates a relatively high Bulk density reached.

The application WO 00/37595 describes a common method Processing of amorphous sodium silicates with other ingredients from detergents or cleaning agents in which aqueous preparations of amorphous sodium silicate and a polymeric carboxylate together with other washing and / or cleaning agent ingredients in one Drying device are sprayed, at the same time with the Drying a granulation can take place, and the resultant basic detergent is then added, if necessary after adding more Ingredients, compacted. The detergents thus produced have comparable primary washing behavior an improved secondary Washability.

The result of different detergent compositions Problem of incrustation or the problem of remaining Detergent residues on washed textiles have so far been eliminated approached in different directions. For example, the pH of the Washing liquor for the precipitation of silicates play an essential role, so that with conventional detergents a certain alkalinity for a good one Washing result is necessary. The pH range is preferably in conventional washing liquors for full detergents above pH 10, for delicates and color detergents between pH 9 and 10. Another approach, the To counteract the failure of the builder substances has so far been the use a larger amount of cobuilders, e.g. B. polymeric polycarboxylates.

The object of the present invention was to provide a detergent to provide that in an ecologically and economically improved manner less incrustation or reduced detergent residues having.

This problem is solved by a detergent or cleaning agent, containing a water-soluble builder, characterized in that the builder has a grain size distribution, the grain sizes of 0.2 to less than 0.4 mm.

In previous detergents, water-soluble builders were used in one Grain size distribution used as it is through the manufacturing process the builder was given. The grain size distribution of the used Builders has not been considered in the prior art, in particular, the grain size was not consistent with that detected precipitation of silicates in the wash liquor, and thus accompanying detergent residues related to the laundry brought.

However, it was surprisingly found that a great deal better detergent result can be achieved if a specific one Grain size range, which is between 0.2 and 0.4 mm grain size, from the builder powder or builder granules used in the detergent Will get removed. Without wishing to be bound by the following theory, can the phenomenon that the dust content (0.2 mm particle size and smaller), or the coarser particles (0.4 mm and larger) one produce much less precipitation on the laundry be explained that the dissolution kinetics of these particles lead to a lower local builder concentration than the dissolution kinetics the average particle size (0.2 to less than 0.4 mm). By the lesser local concentration of the dissolved water-soluble builder tends to less to fail in the form of insoluble precipitation.

A preferred grain size range for the use of the builder in Detergent is either a grain size range of up to 0.2 mm Grain size, or a grain size range of 0.4 to 3 mm, this two grain size fractions in the detergent also at the same time may occur.

In principle, every type is suitable for use as a water-soluble builder suitable from water-soluble builder described so far, in particular amorphous alkali silicates, layered silicates, cogranulates from silicates with polymeric polycarboxylates, carbonate / silicate compounds, cogranulates Layered silicates / non-neutralized polycarboxylates.

The water-soluble builders can be used alone or together with others Builder / co-builder substances are used, the builder substances in can be optimized in such a way that they have a high binding capacity for have divalent ions, e.g. Calcium ions and magnesium ions.

Because builder substances on the one hand as complexing agents, on the other hand in form an ion exchanger can act, the calcium ion concentration, such as also the magnesium ion concentration in the wash liquor due to the Use of suitable builder substances can be reduced. Does it come off water soluble builders e.g. B. silicate, in the wash liquor at low pH increases too quickly, so it can cause insoluble rainfall Calcium or magnesium silicate can be found on the laundry settles. For this reason, as already mentioned above, the pH kept in the wash liquor in the clearly alkaline range, moreover has been a high builder / cobuilder concentration in detergent used.

As suitable cobuilders, which may also be used as compounds with the water-soluble builder substances can be used for example polymeric polycarboxylates from polyacrylic acid or Poly (meth) acrylic acid, or copolymers of these two with any Molar masses, but especially with molar masses over 10,000 g / mol, preferably molar masses from 20,000 to 120,000 g / mol, particularly preferred with 30,000 to 80,000 g / mol. Also suitable copolymeric carboxylates are those of acrylic acid or (meth) acrylic acid with maleic acid. As Copolymers of acrylic acid with maleic acid have been particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% Contain maleic acid. Their relative molecular mass, based on free Acids is generally 2,000 to 70,000 g / mol, preferably 20,000 to 55,000 g / mol and in particular 30,000 to 40,000 g / mol (measured against polyacrylic acid standard). The presence of polymers According to the invention, polycarboxylates are not mandatory necessary, but in one embodiment the builder lies as Particle comprising silicate and polymeric polycarboxylate. On such builder is achieved by spraying an aqueous solution together of water glass / soda with polymeric polycarboxylate in a spray tower and then obtained drying. In another process variant can also use water-soluble alkali silicate together with the polymer can be sprayed and dried. The builder and the cobuilder can However, they are also available individually, i.e. not as a compound according to a further embodiment of the invention side by side in the Detergents or cleaning agents are used. The one obtained from the spray tower Primary good (builder or builder / cobuilder compound) can either be direct processed further, or if necessary e.g. granulated in a compactor and then e.g. in a hammer mill to the desired grain size be ground, with a subsequent to the manufacturing process Grain size from 0.2 to less than 0.4 mm from the product so produced is screened out before it is put into the detergent or cleaning agent is used.

The addition of polymer improves the dirt-bearing capacity of the laundry or detergent, this also contributes to Reduction of precipitation on the laundry. As another Cobuilders can include, for example, copolymers of α-olefins in the detergent and maleic acid, polyaspartic acid, iminodisuccinate or Carboxymethylinuline can be used.

As an additional inorganic builder, finely crystalline, synthetic and bound water-containing zeolite, preferably zeolite A, X, Y and / or P, as well as crystalline layered silicates can be used, which are likewise preferably only present in small amounts. Suitable zeolites are also mixtures of A, X, Y and / or P. As zeolite P, for example, MAP (for example Doucil A24®, commercial product from Ineos) is particularly preferred. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate from zeolite A and zeolite X, which is commercially available as VEGOBOND AX® (commercial product from Condea Augusta SpA). The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 10 to 22% by weight of bound water.

In addition to the zeolites, crystalline, layered sodium silicates corresponding to the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values for x 2, 3 or 4 are included in the means. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M is sodium6 and x is 2 or 3. In particular, both β- and δ-sodium disiliates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.
In addition, phosphate-containing builders can also be used,

Zeolites as well as crystalline layered silicates and phosphates In the agents according to the invention, however, builders are only of of minor importance. In preferred embodiments of the Invention of these substances is less than 5% by weight in total contain. It may even be preferable if they are completely missing, Zeolites in particular often also as powdering agents mixed granules are used, and so in the agents to one may be included in small proportions, although their use as a builder was not intended.

Furthermore, the agents according to the invention contain in preferred Embodiments also alkali carbonates, especially sodium carbonate, and alkali hydrogen carbonates and their mixed salts (sesquicarbonate). It is advantageous for the implementation of the invention if that Weight ratio of alkali carbonate to amorphous sodium silicate in Range 1: 100 to 10: 1, preferably 1:50 to 5: 1. In Embodiments according to the invention can be particularly advantageous be when the weight ratio of alkali carbonate to amorphous Sodium silicate is less than 1.

In addition to the polymeric polycarboxylates, further organic builder substances can be contained in the agents according to the invention. Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycine diacetate (MGDA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 g / mol can be used. A preferred dextrin is described in British patent application 94 19 091. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EPO-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303. WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP-A-0 150 930 and in Japanese patent application JP 93/339896. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight. Further useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.

Another class of substances with cobuilder properties are the Phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. This is among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as Co-builders. It is preferably used as the sodium salt, the Disodium salt neutral and the tetrasodium salt alkaline (pH 9) responding. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in Form of neutral sodium salts, e.g. B. as a hexasodium salt the EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferred as the builder from the phosphonate class used. The aminoalkanephosphonates also have a pronounced Schmermetallbindevermögen. Accordingly, it can, especially if the agents also contain bleach, preferably aminoalkanephosphonates, use in particular DTPMP, or mixtures of the to use the named phosphonates. In addition, everyone can Compounds capable of complexes with alkaline earth ions train as cobuilders. Such organic In the agents according to the invention, cobuilders can be combined with one Proportion of up to 10% by weight, but preferably not more than 5% by weight, be included.

The washing and cleaning agents according to the invention can in addition to mentioned builder substances in principle all known and in such Contain common ingredients. In particular, the 10 to 50% by weight, preferably 15 to 35% by weight, of surfactants, wherein these surfactants are selected from the following groups.

A first group are the anionic surfactants, which at least in Amounts of 0.5% by weight in the agents or Agents produced according to the invention should be included. For this count in particular sulfonates and sulfates, but also soaps.

Preferred surfactants of the sulfonate type are C ₉ -C ₁₃ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C _{12 to} C ₁₈ monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.

Also suitable are alkanesulfonates obtained from C ₁₀ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

The esters of α-sulfofatty acids (ester sulfonates) are also suitable, z. B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids by α-sulfonation of the methyl ester of Fatty acids of plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble Mono salts are made into consideration. Preferably these are the α-sulfonated esters of the hydrogenated Coconut, palm, palm kernel or tallow fatty acids, including sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 % By weight may be present. In particular, α-sulfofatty acid alkyl esters preferred, which is an alkyl chain with no more than 4 carbon atoms have in the ester group, for example methyl esters, Ethyl ester, propyl ester and butyl ester. With particular advantage the methyl esters of α-sulfofatty acids (MES), but also their saponified Disalze used.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which represent mono-, di- and triesters and their mixtures as they do in the production by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained.

As alk (en) yl sulfates, the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₀ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. C ₁₀ -C ₁₆ alkyl sulfates and C ₁₀ -C ₁₅ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates are particularly preferred from a washing-technical point of view. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol ethylene oxide (E0) or C ₁₂ -C ₁₈ -Fatty alcohols with 1 to 4 E0 are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Preferred 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 to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).

Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or its salts, and also ether sulfates (alkylene oxide sulfates) with C _10-18 and 1-7E0.

Other anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (tauride) and / or of N-methyl clycine (Sarcosides) into consideration. Are particularly preferred the sarcosides or the sarcosinates and especially sarcosinates of higher and possibly mono- or polyunsaturated fatty acids such as Oleyl.

Soaps are particularly preferred as further anionic surfactants, preferably in amounts of 0.2 to 5 wt .-% into consideration. Are particularly suitable saturated fatty acid soaps, such as the salts of lauric acid, Myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and Beenic acid and in particular from natural fatty acids, e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures. Along with These soaps or as a substitute for soaps can also be used in the known Alkenyl succinic acid salts are used.

The anionic surfactants (and soaps) can be in the form of their sodium, Potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably lie anionic surfactants in the form of their sodium or potassium salts, in particular in the form of their sodium salts.

The anionic surfactants are in the agents or are preferably used in the process according to the invention in amounts of 1 up to 30% by weight and in particular in amounts of 5 to 25% by weight.

In addition to the anionic surfactants and the cationic, zwitterionic and amphoteric surfactants are preferred above all nonionic surfactants.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 10 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 E0 or 4 E0, C ₉ -C ₁₁ alcohols with 7 E0, C ₁₃ -C ₁₅ alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C ₁₂ -C ₁₈ alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C ₁₂ -C ₁₄ alcohol with 3 E0 and C ₁₂ -C ₁₈ alcohol with 7 E0. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants - as described above - fatty alcohols with more than 12 E0 can also be used. Examples of these are (tallow) fatty alcohols with 14 E0, 16 E0, 20 E0, 25 E0, 30 E0 or 40 E0.

The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G for one Glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.

Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:

in der R³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁴ für einen linearen, verzweigten oder cylcischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R⁵ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht; wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO 95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in which R ^{3 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 represents} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms; where C ₁ -C ₄ alkyl or phenyl radicals are preferred, and [Z] stands for a polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which were preferably prepared by the process described in international patent application WO-A-90/13533. C ₁₂ -C ₁₈ fatty acid methyl esters with an average of 3 to 15 E0, in particular with an average of 5 to 12 E0, are preferred as nonionic surfactants, while, as described above, above all higher ethoxylated fatty acid methyl esters are advantageous as binders. In particular C ₁₂ -C ₁₈ fatty acid methyl esters with 10 to 12 E0 can be used both as surfactants and as binders.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amide may be suitable. The amount these nonionic surfactants are preferably no more than that of the ethoxylated fatty alcohols, especially not more than half from that.

So-called gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds, the two have hydrophobic groups per molecule. These groups are usually separated from each other by a so-called "spacer". This spacer is usually a carbon chain that should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently. Such surfactants stand out generally by an unusually low critical Micell concentration and the ability to control the surface tension of the Greatly reduce water from. In exceptional cases, however, are under the expression Gemini surfactants not only dimeric but also trimeric Understood surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or Dimeral alcohol bis and trimeral cabbage tris sulfates and ether sulfates according to German patent application DE-A-195 03 061. End group sealed dimeric or trimeric mixed ethers according to German patent application DE-A-195 13 391 are particularly characterized by their bi- and multifunctionality out. For example, the end groups capped have surfactants good wetting properties and are low-foaming, so that they are especially for use in machine washing or cleaning processes suitable.

Gemini polyhydroxy fatty acid amides or can also be used Poly-polyhydroxy fatty acid amides, as described in the international patent applications W0-A-95/19953, W0-A-95/19954 and W0-A-95/19955 become.

In addition to surfactants and builders, all of the agents according to the invention can common ingredients in detergents or cleaning agents.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate monohydrate or tetrahydrate and sodium percarbonate are of particular importance. Further bleaching agents that can be used are, for example, peroxypyrophosphates, peroxophthalates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid, phthalimidoperoxohexanoic acid (PAP), or diperdodecanedioic acid. Salts of peracids, such as peroxomonosulfate, can also be used. The bleaching agent content of the agents is 0 to 30% by weight and in particular 5 to 25% by weight, advantageously using perborate monohydrate, tetrahydrate, percarbonate or PAP.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H ₂ O ₂ , preferably multiply acylated alkylenediamines such as N, N'-tetraacylated diamines, acylated glucolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles , triazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates, also Carbonsäureester as p- (alkanoyl) benzenesulfonate, in particular Natriumisononanoyloxybenzolsulfonat, and p- (alkenoyloxy) benzene sulphonates, further caprolactam derivatives, carboxylic acid anhydrides such as phthalic anhydride and esters of polyols such as glucose pentaacetate. Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0 525 239, and acetylated pentaerythritol. The bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.

Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and actylated sorbitol-mannitol mixtures (SORMAN). The Bleach activator can be coated with coating substances in a known manner or, if necessary, using auxiliaries, in particular methyl celluloses and / or carboxymethyl celluloses, granulated or extruded / pelleted have been and, if desired, other additives, for example dye. Preferably contains one Granules over 70% by weight, in particular from 80 to 99% by weight Bleach activator. A bleach activator is preferably used, the forms peracetic acid under washing conditions. Also quaternized Aminoalkyl nitriles or acetonitrile derivatives can be used as bleach activators be used. Another preferred bleach activator is a Morpholinonitrilequat, or a quaternized glycine nitrile, as in EP 0 941 299.

In addition to the conventional bleach activators listed above or in their place can also those from the European Patents EP 0 446 982 and EP 0 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes be included as so-called bleaching catalysts. To the in Transition metal compounds in question include in particular those German patent application DE 195 29 082 known manganese, iron, Cobalt, ruthenium or molybdenum salt complexes and their from German patent application DE 196 20 267 known N-analog compounds, the manganese known from German patent application DE 195 36 082, Iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German patent application DE 196 05 688 manganese, iron, Cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, from the German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium amine complexes, that in German patent application DE 44 16 438 manganese, copper and cobalt complexes described in the European patent application EP 0 272 030 described cobalt complexes, the manganese complexes known from European patent application EP 0 693 550, those known from European Patent EP 0 392 592 Manganese, iron, cobalt and copper complexes and / or those in the European patent EP 0 443 651 or the European Patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, Manganese complexes described in EP 0 549 272, EP 0 544 490 and EP 0 544 519, Combinations of bleach activators are for example the German patent application DE 196 13 103 and the international Patent application WO 95/27775 known. Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on entire means used.

Enzymes which may be contained in agents according to the invention include Proteases, amylases, pullulanases, cellulases, cutinases and / or Lipases, for example proteases such as Properase®, Alcalase®, BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl®, Purastar®, Kenzym®, Purastar® Ox Am, cellulases such as Celluzyme®, Carezyme®, KAC® and / or those from the international Patent applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase®, Lipomax®, Lumafast®, Lipoprime®, Lipex® and / or Lipozym®. The enzymes used can be such. Tie international patent applications WO 92/11347 or WO 94/23005 described, adsorbed on carriers and / or in coating substances embedded to protect them against premature inactivation. she are preferably in in washing and cleaning agents according to the invention Quantities up to 10% by weight, in particular from 0.05% by weight to 5% by weight contain, with particular preference against oxidative degradation stabilized enzymes such as z. B. from the international Patent applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350 are known can be used.

In addition, the agents can also contain components which and positively influence fat washability from textiles. This The effect becomes particularly clear when a textile is soiled already several times with a detergent according to the invention, the contains this oil and fat-dissolving component, was washed. To the preferred oil and fat dissolving components include, for example nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether, and those from the prior art known polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Particularly preferred from these are the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. B. from silicone, paraffins or waxes.

The foam inhibitors are preferably silicone and / or paraffin-containing foam inhibitors, to a granular, water-soluble or dispersible carrier substance bound. In particular are there Mixtures of paraffins and bistearylethylenediamides are preferred.

Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and keep it moving to prevent the dirt. Water-soluble colloids are usually used for this suitable organic nature, for example the water-soluble salts polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or Ether sulfonic acids of starch or cellulose or salts of acid Sulfuric acid esters of cellulose or starch. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Soluble starch preparations and others other than those above can also be used use mentioned starch products, e.g. B. degraded starch, Aldehyde starches, etc. Graying inhibitors are commonly used in Amounts of 0.1 to 5 wt .-%, based on the agent used.

As a further additional component, the invention Textile detergent formulation usual color transfer inhibitors in the amounts usual for this (about 0.1 to 2 wt .-%) contain.

Color transfer inhibitors are, for example, homo- and Copolymers of vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone and 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000 and cross-linked, finely divided polymers based on these monomers used. The use of such polymers mentioned here is known see. DE-B 22 32 353, DE-A 28 14 287, DE-A 28 14 329 and DE-A 43 16 023.

Preference is given to using Polyvinyl pyrrolidone, especially in the form of PVP granules. Farther cellulose ethers such as carboxymethyl cellulose (sodium salt) are preferred, Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as Methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methyl carboxymethyl cellulose and mixtures thereof.

The agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar connections, which instead of the morpholino group is a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Brighteners of the type of substituted Diphenylstyryle be present, e.g. B. the alkali salts of 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

In addition to the ingredients mentioned, the agents can also do other things known, usually in washing, rinsing or cleaning agents additives used, for example small amounts of neutral Filling salts as well as colors and fragrances and opacifiers.

The remaining washing, cleaning and other ingredients of the Detergents can be used as powder, granulate or cogranulate are, their particle size in a range of 1 to 2500 microns, is preferably from 5 to 1000 microns, or they can be used as a liquid component be added.

The washing or cleaning agent according to the invention can be in the form of a powder Granules or as a compact, in addition, the washing or Detergent provided in the form of a pressed molded body become.

The use of a builder / co-builder with a particular Particle size distribution, as in the present application has the advantage that no precipitation, or low Detergent residues on the laundry after the washing process has ended can be found. This is especially the case if the Wash liquor has a pH below pH 10. A preferred pH range for using the builders with the one described here Grain size distribution is a range from pH 8 to pH 12.

In addition, by better "trapping" of divalent ions, in particular Ca ²⁺ and Mg ²⁺ , the enzyme performance of the proteases used is significantly improved by the builders of the particle size distribution according to the invention, so that an improvement in the washing result is also achieved in this regard.

Therefore, the use of builder substances with the grain size distribution shown in this application has a much wider range of uses than was previously possible. A much wider range of different detergent compositions can also be used, e.g. B. Too high a content of hydrogen carbonate has hitherto led to precipitation of SiO ₂ , while the use of the builder substances in particle size ranges, as indicated in the present application, largely independently of the hydrogen carbonate (H ₂ CO ₃ ) addition lead to desired washing results ,

The following examples are intended to illustrate the invention and its effect explain without the invention merely referring to the here shown compositions limited.

Examples Example 1: Detergent formulations: composition

Various detergent formulations with a focus on builders of any grain size and screened builders.

Example 2

Bag test with detergent formulations containing different ones Builder fractions according to example 1

Description of the sachet test:

In a dark terry bag (20 * 20cm / blue / black) that will Washing powder sewn in. The following dosage is used: HBII / normal dirty, then the bag is washed with 3.7 kg ballast Normal program washed at 30 ° C. The water hardness of tap water is 15 ° dH. After washing, the terry bag is cut open, turned to the left and visually viewed the amount of residues.

The solubility of a detergent formulation can be assessed on the basis of the amount of residue. A good reference has no residues.

Example 3

Wool test: proteolytic effectiveness depending on the Builder performance: The more effective a protease is, the more effective it is Ca2 + and Mg2 + - ions are removed from the wash liquor. The better one Builder works, the more effective these ions from the wash liquor become away.

Principle:

This method will take advantage of the molecular structure of the wool made. The fibrous wool is one of the so-called keratins proteins essentially crosslinked by cysteine disulfide bridges represent. The basic building blocks of wool are amino acids that over Peptide bonds are linked together. Thus, the wool can be used as Substrate for the protease can be considered. The mining performance of the peptide-cleaving enzymes are determined gravimetrically and reflected indirectly the activity of the protease again. The protease activity will heavily influenced by builder performance. The better the builder acts, the faster and stronger the wool becomes from the protease decomposed.

reagents: 10 * 10cm IWS wool

Products with a defined protease concentration without bleach. The bleach inhibits protease activity, causing the Test would take too long.

Equipment:

The test is carried out in the Linitest (laboratory tester), with eight Sample containers is equipped.

Execution:

A 10 * 10cm wool fabric is cut and labeled for each product. The The wool is labeled with a sewn-on protease-stable Cotton fabric piece. The wool is washed with 200ml water (HBII) and 1g Test product washed. This process is repeated until in the Wool holes can be seen. In addition, after 5, 10, 15 and 20. laundry weighed dry, and the mass loss in Comparison to the respective initial value determined in%. Once a good one Differentiation is possible, washing can be stopped. In this The test was carried out on all test products 1% Everlase 12.0 T from Novo added.

Evaluation:

The product that causes the greatest mass loss shows the best Builder performance.

Comment & conclusion:

The formulations with the preferred builder fractions show a higher proteolytic activity and thus the more effective removal of Ca / Mg 2+ ions in the washing process (see table).

Example 4 Detergent formulations: compositions

Different detergent formulations with a focus on: different concentrations of the other ingredients.

Example 5

Bag test with detergent formulations according to Example 4

Claims (12)

Detergent or cleaning agent containing a water-soluble builder, characterized in that the builder has a particle size distribution which excludes particle sizes from 0.2 to less than 0.4 mm. Detergent or cleaning agent according to claim 1, characterized in that the builder has a grain size of up to 0.2 mm and / or from 0.4 to 3 mm. Washing or cleaning agent according to claim 1 or 2, characterized in that the water-soluble builder is selected from amorphous alkali silicates, layer silicates, cogranulates from silicates with polymeric polycarboxylates, carbonate / silicate compounds and cogranulates from layer silicates / non-neutralized polycarboxylates. Detergent or cleaning agent according to one of claims 1 to 3, characterized in that in addition to the water-soluble builder, there are further builder and / or cobuilders in the detergent or cleaning agent. Detergent or cleaning agent according to one of claims 1 to 4, characterized in that the other detergents and cleaning agents have a particle size of up to 2500 µm and are present as powder, granules or cogranules. Washing or cleaning agent according to one of claims 1 to 5, characterized in that the washing or cleaning agent is present as a compact. Detergent or cleaning agent according to one of claims 1 to 6, characterized in that the detergent or cleaning agent is in the form of a pressed molded body. Use of a water-soluble builder in a washing or cleaning agent, characterized in that the builder is used in the washing or cleaning agent in a particle size distribution that excludes a particle size of 0.2 to less than 0.4 mm. Use according to claim 8, characterized in that the builder is used in a grain size distribution which comprises grain sizes of up to 0.2 mm and / or from 0.4 mm to 3 mm. Use according to claim 8 or 9, characterized in that in addition to the water-soluble builder, other builders / cobuilders are used, if appropriate also as cogranulate with the water-soluble builder. Process for producing a detergent or cleaning agent, characterized in that builders with a particle size distribution of up to 0.2 mm and / or from 0.4 to 3 mm are used in the detergent or cleaning agent. Use of a detergent or cleaning agent according to one of the Claims 1 to 7 in a pH range for the wash liquor of pH 8 up to pH 12.