EP1416039B1 - Use of water soluble builders with a specific particle size in bleach free laundry detergents - Google Patents

Abstract

Use is claimed in bleach-free detergents of water-soluble builders which have a particle size distribution such that particles of sizes from 0.2 to below 0.4 mm are excluded.

Description

The present invention relates to the use of water-soluble builders in bleach-free detergents, especially in fine and color detergents, wherein the builder has a certain particle size distribution, are excluded in the grain sizes of 0.2 mm to less than 0.4 mm.

Builders or cobuilder systems are among the most important classes of substances for the construction of detergents or cleaners. They fulfill various tasks in the washing or cleaning agents, which include water softening, enhancing the washing effect, a grayness inhibition and the dirt dispersion. In addition, the builders are expected to contribute to the alkalinity necessary for the washing process, to exhibit high absorbency for surfactants and / or other detergent additives, to improve the effectiveness of surfactants, and to contribute to the postive properties of solid products in powder form, for example, structure formation Control of the dust problem. In some cases, the different requirements can not be met with just one builder component alone, so in these cases, a system of builders and co-builders is used.

Earlier water-soluble builders based on phosphorus and / or nitrogen have come under criticism for ecological reasons, whereupon a change to three-dimensionally crosslinked, water-insoluble builders, eg. As zeolites, took place. However, with water-insoluble builders, the phenomenon of undesired incrustation, which requires the co-use of co-builders, occurs to an increased degree. For example, together with zeolites, polymeric polycarboxylates, especially copolymers based on (meth) acrylic acid, are frequently used today and maleic acid used together with soda. In addition, complexing agents are often used.

Concurrently with the development of zeolite NaA as a builder, it has been proposed to use selected water-soluble amorphous sodium silicate compounds as builders in detergents or cleaners. By way of example, the U.S. Patents 3,912,649 . 3,956,467 . 3,838,193 and 3,879,527 to be named. Herein, amorphous sodium silicate compounds are described as builders prepared by spray-drying aqueous waterglass solutions, then grinding and compacting with additional dehydration of the millbase.

The EP-A-0 444 415 describes a detergent having from 0.5 to 60% by weight of a builder, from 5 to 50% by weight of a surfactant and further customary auxiliary detergents, the builder comprising an amorphous, low-sodium disilicate having a water content of from 0.3 to 6% by weight. represents. The preparation of these highly dehydrated amorphous disilicates is carried out in a multi-stage process, which initially provides for the preparation of a pulverulent amorphous sodium silicate with a water content of 15 to 23% by weight. This material is treated in a rotary kiln with flue gas at temperatures of 250 to 500 ° C. The sodium disilicate emerging from the rotary kiln is comminuted to particle sizes of 0.1 to 12 mm with the aid of a mechanical crusher and then ground to particle sizes of 2 to 400 μm.

The patent applications WO 96/20269 and WO 97/34977 describe both amorphous alkali metal silicates, which are exposed to ingredients of detergents or cleaners, in particular ingredients (eg surfactants) in liquid form. In both applications a relatively high bulk density is achieved by the addition and granulation of the silicates.

The registration WO 00/37595 describes a process for the co-processing of amorphous sodium silicates with other ingredients from detergents or cleaners, in which aqueous preparations of amorphous sodium silicate and a polymeric carboxylate are sprayed together with other detergents and / or cleansing ingredients in a drier, simultaneously with drying a granulation can take place, and the resulting basic detergent is then compacted, possibly after admixing other ingredients. The detergents produced in this way have an improved secondary detergency with comparable primary washing behavior.

The problem of incrustation resulting from various detergent compositions, or the problem of remaining detergent residues on laundered fabrics has hitherto been approached from different directions. Thus, for example, the pH of the wash liquor plays a significant role in the precipitation of silicates, so that with conventional detergents a certain alkalinity is necessary for a good washing result. The pH range in conventional washing liquors is preferably above pH 10 for heavy-duty detergents and between pH 9 and 10 for fine and color detergents. Another approach to counteract precipitation of the builders has hitherto been the use of a relatively large amount of cobuilders, eg. B. polymeric polycarboxylates.

The object of the present invention was to provide improved bleach-free (gentle) detergents which have a good stain removal and a very good soil-carrying capacity with simultaneously improved care properties for the laundry.

This object is achieved by the use of a water-soluble builder in bleach-free detergents, characterized in that the Builder has a grain size distribution comprising the grain sizes of 0.4 to 3 mm, but excludes grain sizes from 0.2 to less than 0.4 mm.

In previous detergents, water-soluble builders were used in a particle size distribution as dictated by the manufacturing process of the builder. The particle size distribution of the builder used has not been considered further in the prior art.

It has surprisingly been found that a very good washing result with simultaneously improved care properties for the laundry can be achieved if a specific grain size range of the builder, which is between 0.2 to less than 0.4 mm grain size, is removed from the builder powder or builder granulate used in the bleach-free detergent ,

The builder preferably has a particle size distribution of 0.4 to 3 mm.

In principle, any type of water-soluble builder described hitherto is suitable for use as a water-soluble builder, in particular amorphous alkali silicates, layered silicates, cogranulates of silicates with polymeric polycarboxylates, carbonate / silicate compounds, cogranules of phyllosilicates / unneutralized polycarboxylates.

The water-soluble builders may be used alone, or in conjunction with other builder / co-builders, wherein the builders may be optimized to have a high binding capacity for divalent ions, such as calcium ions and magnesium ions.

Since builders act on the one hand as a complexing agent, on the other hand in the form of an ion exchanger, the calcium ion concentration, as well as the magnesium ion concentration in the wash liquor can be reduced by the use of suitable builders. Dissolves the water-soluble builder, eg. As silicate, in the wash liquor at low pH all too quickly, it may cause precipitation of insoluble calcium or magnesium silicate, which settles on the laundry. For this reason, the pH in the wash liquor has hitherto been kept in the clearly alkaline range, as has already been mentioned above, and until now a high builder / cobuilder concentration has been used in the detergent.

For the care of sensitive laundry (fine and colored laundry), however, it is not desirable to have to adjust the pH in a very alkaline range, since in particular sensitive tissue can be significantly attacked. Thus, it is desirable in particular in mild detergents to be able to adjust the pH in a relatively low range, in order to give the washing agent good care properties combined with good washing action. The preferred pH range in the wash liquor is for fine and color detergents according to the invention at pH 8 to 10, in particular at pH 8.5 to 9.5.

Suitable co-builders which can optionally also be used as compounds with the water-soluble builders are, for example, polymeric polycarboxylates of polyacrylic acid or poly (meth) acrylic acid, or copolymers of these two having arbitrary molecular weights, but in particular having molecular weights above 10,000 g / mol, preferably molar masses of 20,000 to 120,000 g / mol, more preferably 30,000 to 80,000 g / mol. Additionally suitable copolymeric carboxylates are those of acrylic acid or (meth) acrylic acid with maleic acid. Particularly suitable copolymers of acrylic acid with maleic acid have proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% Contain maleic acid. Their molecular weight relative to 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 polymeric polycarboxylates is not essential to the invention, but in one embodiment the builder is present as a particle comprising silicate and polymeric polycarboxylate. Such a builder is obtained by co-spraying an aqueous solution of water glass / soda with polymeric polycarboxylate in a spray tower and then drying. In another variant of the method, water-soluble alkali metal silicate can also be sprayed and dried together with the polymer. However, the builder and the co-builder can also be present individually, ie not as a compound, but according to a further embodiment of the invention are used side by side in the washing or cleaning agent. The primary product (builder or builder / cobuilder compound) obtained from the spray tower can either be further processed directly, or granulated, for example, in a compact and then ground, for example, in a hammer mill to the desired particle size, followed by the production process, a particle size of 0.2 to less than 0.4 mm is screened from the product thus prepared before this is used in the detergent or cleaning agent.

The so prepared and screened-out builders have a good dirt-carrying capacity. In previous detergent formulations, zeolites were commonly used to impart good soil-carrying ability to the detergent. However, zeolites have the disadvantage that they adsorb well not only the dirt contained in the wash liquor, but also the surfactants used in the detergent, whereby they are "taken out" as active substances from the wash liquor. For this reason, when using zeolites in the detergents, much more surfactants must be incorporated into the detergent formulations used when using water-soluble builders. This plays a role in particular in color detergents in which a good foaming for the color care is desired. However, since surfactants are on the one hand polluting to the environment, and on the other hand cost-intensive, it is particularly desirable to keep the amount of surfactants used as low as possible without impairing the washing result.

Water-soluble builders also have a good soil-carrying capacity, but they remove the surfactants used to a much smaller extent from the wash liquor than the zeolites. The insoluble and finely dispersed zeolite particles have a high surface area at which e.g. adsorb washing-active substances such as surfactants during the washing process. In particular, in the case of the low washing temperatures typical of fine and color detergents, the wash liquor thereby very poorly depletes surfactants, so that the cleaning performance decreases, or compensation must be made by a higher dosage of surfactants. At the water-soluble builders, the washing-active substances are only adsorbed at the beginning of the washing process from the wash liquor. However, since the silicates described are completely dissolved in the course of the washing process, the surfactants are also fully available for the cleaning process.

The addition of polymer additionally improves the soil-carrying capacity of the detergent and also contributes to the further reduction of rainfall on the laundry. Copolymers of α-olefins and maleic acid, polyaspartic acid, iminodisuccinates or carboxymethylinulines can be used as further co-builders in the detergent.

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

In addition to the zeolites, crystalline, layered sodium silicates according 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 to be included in the compositions. Such crystalline layered silicates are described, for example, in US Pat European Patent Application EP-A-0 164 514 described. Preferred crystalline layered silicates of the formula given are those in which M is sodium 6 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,

However, both zeolites and crystalline layered silicates and phosphate-containing builders are only of minor importance in the agents according to the invention. In preferred embodiments of the invention, less than 5% by weight of these substances are contained in total. It may even be preferred if they are completely absent, in particular zeolites are often used as a powdering agent on blended granules, and thus may be included in the agents to a small extent, although their use as a builder was not intended.

Furthermore, in preferred embodiments, the agents according to the invention also contain alkali metal carbonates, in particular sodium carbonate, and also alkali hydrogen carbonates and their mixed salts (sesquicarbonate). It is advantageous for the practice of the invention if the weight ratio of alkali metal carbonate to amorphous sodium silicate in the range 1: 100 to 10: 1, preferably 1:50 to 5: 1, is located. In embodiments according to the invention, it may be particularly advantageous if the weight ratio of alkali metal carbonate to amorphous sodium silicate is less than 1.

In addition to the polymeric polycarboxylates, the compositions according to the invention may contain further organic builders. Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of 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), methylglycine diacetate (MGDA), if such use is not objectionable for ecological reasons, and mixtures thereof. 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 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. Further suitable builder substances are polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in US Pat European Patent Application EP-A-0 280 223 described, can be obtained. 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. Further 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. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, 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 common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and also so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2,000 to 30,000 g / mol. A preferred dextrin is in the British Patent Application 94 19 091 described. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of at least one alcohol function of the saccharide ring To oxidize carboxylic acid function. Such oxidized dextrins and methods of their preparation are 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 as well as the 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 known. Also suitable is an oxidized oligosaccharide according to German patent application DE-A-196 00 018 , A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. This Ehtylendiamin-N, N'-disuccinate (EDDS), the synthesis of which, for example, in US 3,158,615 is described, preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in the US Pat US 4,524,009 . US 4,639,325 , in the European Patent Application EP-A-0 150 930 and the Japanese Patent Application JP 93/339896 to be discribed. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%. Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present 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 co-builders are described, for example, in the international patent application WO 95/20029 described.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). responding. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced Schmermetallbindeabmögen. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders. Such organic cobuilders may be present in the compositions according to the invention in a total amount of up to 10% by weight, but preferably not more than 5% by weight.

In addition to the builders mentioned, the detergents according to the invention may in principle contain all known ingredients customary in such agents. In particular, the compositions contain from 10 to 50% by weight, preferably from 15 to 35% by weight, of surfactants, these surfactants being selected from the following groups.

A first group are the anionic surfactants, which should be present in at least 0.5% by weight in the compositions according to the invention or agents prepared according to the invention. These include in particular sulfonates and sulfates, but also soaps.

As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C _{12 to} C ₁₈ monoolefins with terminal or internal double bond Sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.

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

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), z. As the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids prepared by α-sulfonation of methyl esters 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 be considered. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-sulfo fatty acids (MES), but also their saponified disalts are used.

Other suitable Anionentenside are sulfated Fettsäureglycerinester which mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.

Alk (en) ylsulfates are, for example, the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₀ -C ₁₈ fatty alcohols from coconut fatty 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. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. For washing-technical interest, C ₁₀ -C ₁₆ -alkyl sulfates and C ₁₀ -C ₁₅ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates are particularly preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and 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 -C ₂₁ -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ Fatty alcohols containing 1 to 4 EO are suitable. They are used in detergents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the 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 of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Again, sulfosuccinates whose fatty alcohol residues are of ethoxylated fatty alcohols with narrow homolog distribution derive, more preferably. 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 well as ether sulfates (alkylene oxide sulfates) with C _10-18 and 1-7E0.

Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylclycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.

As further anionic surfactants in particular soaps, preferably in amounts of 0.2 to 5 wt .-% into consideration. Particularly 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 from natural fatty acids, for. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.

The anionic surfactants (and 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. Preferably, anionic surfactants are in the form of their sodium or potassium salts, especially in the form of their sodium salts.

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

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

The nonionic surfactants used are preferably 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 can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, are Akoholethoxylate with linear radicals of alcohols of natural origin having 10 to 18 carbon atoms, eg. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. 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 EO, 5 EO, 7 EO or 8 EO , C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 E0 and C ₁₂ -C ₁₈ -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, as described above, fatty alcohols containing more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a Glykoseeinheit with 5 or 6 C-atoms, preferably for glucose. The degree of oligomerization x, which is the Indicating the distribution of monoglycosides and oligoglycosides, any number - which can also be taken as an analytically determined quantity - is between 1 and 10; preferably x is 1.2 to 1.4.

Also suitable are polyhydroxy fatty acid amides of the formula (I) in which R ^{1 is} CO for 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 having 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 having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in the R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or a Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms; wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred, and [Z] is a polyhydroxyalkyl radical whose alkyl chain has at least two Is substituted hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also obtained here preferably 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 be used, for example, according to the teaching of the international patent application WO 95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide.

Another class of preferred nonionic surfactants 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 from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in the Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 were prepared. Preferred nonionic surfactants are C ₁₂ -C ₁₈ fatty acid methyl esters having on average from 3 to 15 EO, in particular having an average of from 5 to 12 EO, while, as binders, as described above, especially higher ethoxylated fatty acid methyl esters are advantageous. In particular, C ₁₂ -C ₁₈ fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.

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 the ethoxylated fatty alcohols, especially not more than half of them.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.

Examples of suitable gemini surfactants are sulfated hydroxy mixed ethers according to US Pat German patent application DE-A-43 21 022 or dimer alcohol bis and trimeralcyl tris sulfates and ether sulfates according to the German patent application DE-A-195 03 061 , End-capped dimer or trimeric mixed ethers according to the German patent application DE-A-195 13 391 They are characterized by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.

However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in international patent applications WO 95/19953 . WO 95/19954 and WO 95/19955 to be discribed.

In addition to surfactants and builders, all ingredients customary in detergents or cleaners can occur in the compositions according to the invention.

Among the optionally included in the inventive compositions enzymes include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as Properase®, BLAP ^®, Optimase ^®, Opticlean ^®, Maxacal ^®, Maxapem ^®, Durazym ^®, Alcalase ^{® ®,} Purafect ^® 0XP, Esperase ^® and / or Savinase ^®, amylases such as Termamyl ^®, amylase LT, Maxamyl ^®, Duramyl ^®, Purastar® ^®, Kenzym ^®, Purastar® ^® Ox Am, cellulases as Celluzyme ^®, Carezyme ^®, KAC ^® and / or from 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, such as. In international patent applications WO 92/11347 or WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05% by weight to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation, as described, for example, in US Pat. B. from the international patent applications WO 94/02597 . WO 94/02618 . WO 94/18314 . WO 94/23053 or WO 95/07350 are known to be used.

Additionally, the compositions may also contain components that positively affect oil and grease washability from fabrics. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. Examples of preferred oil and fat dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as 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 thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. As 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 foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. With advantages, mixtures of different foam inhibitors are used, for. As those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.

Grayness inhibitors have the task to keep suspended from the fiber debris suspended in the fleet and so prevent the re-raising of the dirt. 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 carboxylic acids or ether sulfonic acids of starch or of 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 can be use starch products mentioned, for. As degraded starch, aldehyde levels, etc .. Graying inhibitors are usually used in amounts of 0.1 to 5 wt .-%, based on the means.

As a further additional constituent, the textile detergent formulation according to the invention may comprise customary color transfer inhibitors in the quantities customary for this purpose (about 0.1 to 2% by weight).

As color transfer inhibitors, for example, homopolymers and copolymers of vinylpyrrolidone, of vinylimidazole, of vinyl oxazolidone and of 4-vinylpyridine N-oxide having molecular weights of from 15,000 to 100,000 and crosslinked finely divided polymers based on these monomers are used. The use of such polymers mentioned here is known, cf. DE-B 22 32 353 . DE-A 28 14 287 . DE-A 28 14 329 and DE-A 43 16 023 ,

The use of polyvinylpyrrolidone, in particular in the form of PVP granules, is preferred in the agents according to the invention. Also preferred are cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

The agents may contain as optical brighteners derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. Suitable z. B. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of substituted Diphenylstyryle be present, for. Example, the alkali salts of 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brightener can be used.

In addition to the ingredients mentioned, the compositions may also contain other known additives commonly used in detergents.

The other washing and other ingredients of the detergent can be used as powder, granules or cogranules, wherein the particle size is in a range of 1 to 2500 .mu.m, preferably from 5 to 1000 microns, or they can be added as a liquid component.

The detergent according to the invention can be present as a powder, as a granulate or as a compact, and the detergent can also be provided in the form of a pressed molding.

• 15 - 45% wasserlöslichen Builder
• 5 - 20% Soda
• 0 - 15% Sesquicarbonat
• 3 - 20% Citrat oder Zitronensäure
• 3 - 10% nichtionisches Tensid
• 3 - 16% anionisches Tensid
• 0 - 5% Seife
• 0 - 6% Polycarboxylat
• 5 - 35% Sulfat
• 1 - 10% Additive, ausgewählt aus Enzymen, Entschäumer, Öllösepolymer, Carboxymethylcellulose, Parfum, Phosphonaten, Farbübertragungsinhibitoren.

Particularly preferably, a detergent of the present invention comprises the following components:

• 15-45% water-soluble builder
• 5 - 20% soda
• 0 - 15% sesquicarbonate
• 3 - 20% citrate or citric acid
• 3 - 10% nonionic surfactant
• 3 - 16% anionic surfactant
• 0 - 5% soap
• 0-6% polycarboxylate
• 5 - 35% sulphate
• 1-10% additives selected from enzymes, defoamers, oil-soluble polymer, carboxymethylcellulose, perfume, phosphonates, color transfer inhibitors.

The use of a builder / cobuilder with a certain particle size distribution, as described in the present application, in bleach-free detergents, especially in fine and color detergents has the advantage that the detergents have a good stain removal and a high soil-carrying capacity, so a good Washing result, at the same time be awarded very good care properties. In addition, there is no precipitation in the wash liquor, or less detergent residues on the laundry after completion of the washing process. This is particularly the case when the wash liquor has a pH below pH 10, as is desired especially in mild detergents.

In addition, the enzyme performance of the proteases used is significantly improved by a better "interception" of divalent ions, in particular Ca ²⁺ and Mg ²⁺ , by the builder 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 builders with the particle size distribution shown in this application has a much wider range of applications than was previously possible. Also, a much broader range of different detergent compositions can be used, e.g. For example, too high a content of bicarbonate has so far led to precipitation of SiO ₂ , while the use of the builders in particle size ranges, as indicated in the present application, largely independent of the bicarbonate (H ₂ CO ₃ ) addition lead to desirable wash results ,

The following examples are intended to explain the invention and its effect in more detail, without the invention being limited to the compositions shown here.

Examples

Application of water-soluble builders of specific particle size in mild detergent and color detergent.

Example 1: Fine detergent formulations

Ingredients in% 1.1 1.2 1.3 1.4 1.5 1.6 1.7 Amorphous silicate> 0.4mm 31 25 25 20 20 15 Sodium aluminum silicate 48 soda 18 9 9 20 16 16 8th sesquicarbonate 12 12 trisodium citrate 15 17 citric acid 12 9 9 4 4 5 5 sulfate 7 14.5 14.5 33.5 14.5 14.5 5 Alcohol ethoxylate 4 6 5 6 5 4 5 Fatty alcohol sulfate 15 14 11 9 15 16 alkylbenzenesulfonate 17.5 Soap 2 2 4 2 2 2 4 APG 2.5 2 2 polycarboxylate 3 3 3 2 3 3 5 Other additives * ad 100 5.5 5.5 5.5 3.5 5.5 5.5 2.5 * For example: enzymes, defoamers, oil-soluble polymer, perfume, phosphonates, dye transfer inhibitor, carboxymethylcellulose

Example 2: Color detergent formulations

Inhalants in% 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 Amorphous silicate> 0.4mm 35 35 40 30 30 30 30 Sodium aluminum silicate 45 soda 5 5 5 5 10 sesquicarbonate 15 15 15 citric acid 10 10 10 10 10 10 10 6 sulfate 8th 15 9 28 25 24.5 24 8.5 Alcohol ethoxylate 10 6 4 6 6 6 6 9.5 Fatty alcohol sulfate 9 7 10 14 14 14 14 10.5 phosphonate 0.5 0.5 CMC 1 Polyearboxylat 6 5 5 3 3 3 3.5 Other additives * ad 100% 7 7 7 7 7 7 7 7 * For example: enzymes, defoamers, oil-soluble polymer, perfume, color transfer inhibitor, speckles

Example 3: mild detergent washing performance Part 1: Stain removal 1a: stain removal on natural stains Washing conditions: washing machine / HBII / 40 ° C / 3 pre-wash / 5 passes / dosage normally dirty

Conclusion: The use of water-soluble builders of certain particle size leads to an increase in the overall washing performance of the mild detergents.

Example 3: mild detergent, washing action Part 1: Stain removal 1b: stain removal on artificial stains Washing conditions: washing machine / HBII / 40 ° C / 3 passes / 2 replicates / dosage normally dirty

Evaluation: the higher the remission value achieved, the better the washing effect achieved.

Conclusion: It can also be seen on artificial stains that the use of water-soluble builders of specific particle size leads to an increase in the overall washing performance of the mild-duty detergents.

Example 3: mild detergent washing performance Part 2: Dirt carrying capacity Washing conditions: washing machine / HBII / 40 ° C / 15 passes / dosage normally dirty

example 3.8 3.9 3.10 Waschmittelformullerung 1.1 1.2 1.7 Multi washing textiles Greenish value (Y value) 15 washes Standard cotton fabric 90.8 91.2 90.2 terry 87.4 87.1 88.0 Single Jersey (Modal) 88.8 88.8 89.0 Polyester / cotton fabric 84.3 84.1 84.7 polyester 87.8 87.9 87.7 polyamide 87.2 87.6 87.9

Assessment: the higher the white value obtained, the better the soil-carrying capacity of the detergent formulation used.

Conclusion: With improved stain removal performance, the soil-carrying capacity of the formulations, which use water-soluble builders of certain particle size, remains the same order of magnitude as that of zeolite-containing formulations.

Example 3: mild detergent washing performance Part 3: Care properties 3a: color care properties Washing conditions: washing machine / HBII / 30 ° C / 10 passes / dosage normally dirty / care short program

example 3.11 3.12 Waschmittelfomulierung 1.2 1.7 instrumental Gray scale grades * Denim cotton black 4.5 3.5 Cotton direct dye red 4.5 4 Cotton direct dye green 4.5 4 Cotton direct dye purple 3 2.5 * Grade 5 = good / grade 1 = poor

Conclusion: The use of water-soluble builders of certain particle size leads to improved color retention, especially on dark textiles.

Example 3: mild detergent washing performance Part 3: Care properties 3b: fabric care properties Washing conditions: washing machine / HBII / 30 ° C / 10 passes / dosage normally dirty / care short program

Conclusion: The use of water-soluble builders of certain particle size leads to an improvement of the textile properties, in particular lower abrasion, creases and residues. In soft touch, the formulations are comparable to zeolite-based formulations.

Example 4: Color detergent washing performance Part 1: Stain removal 1a: stain removal on natural stains Washing conditions: washing machine / HBII / 40 ° C / 3 pre-wash / 5 passes / dosage normally dirty

Conclusion: The use of water-soluble builders of certain particle size leads to an increase in the overall washing performance of the color detergents, even with less use of the washing-active substances (surfactants).

Example 4: Color detergent washing performance Part 1: Stain removal 1b: stain removal on artificial stains Washing conditions: washing machine / HBII / 40 ° C / 3 passes / 2 replicates / dosage normally dirty

example 4.5 4.6 4.7 4.8 detergent formulation 2.1 2.2 2.3 2.8 Stains on BW Remmisionwert wavelength tea 53.6 53.0 52.8 53.4 540 nm Wine 70.6 71.5 72.5 70.2 540 nm Pigment / nut oil / milk 72.9 70.6 70.8 71.9 460 nm WFK standard 56.5 53.8 53.9 54.8 460 nm Carbon black / olive oil 31.2 31.2 29.1 32.4 540 nm lipstick 61.0 58.8 58.0 56.4 550 nm cocoa 54.0 51.2 54.4 53.8 460 nm blood 69.8 65.7 67.4 58.0 540 nm mineral oil 39.8 36.7 39.4 40.2 540 nm coffee 61.8 62.2 62.1 62.3 540 nm grass 67.5 66.9 66.6 67.2 460 nm butter 51.2 51.1 50.9 52.9 480 nm

Evaluation: the higher the remission value, the better the washing performance of the formulation used.

Conclusion: The use of water-soluble builders of certain particle size leads to a comparable washing performance, even with a very small amount of washing-active substances.

Example 4: Color detergent washing performance Part 2: Dirt carrying capacity Washing conditions: Linitest / HBII / 60 ° C / 7 washes / dosage normally dirty

example 4.9 4.10 4.11 4.12 4.13 Waschmntelformulierung 2.4 2.5 2.6 2.7 2.8 Multi washing textiles Basic white value (Y value) 7 washes Standard fabric cotton 84 83 85 85 86 Standard fabric polyester / cotton 84 84 83 84 85 Standard fabric polyester 79 79 79 79 82

Evaluation: the higher the white value, the better the soil-carrying capacity of the formulation used.

Conclusion: With improved performance in the stain removal remains the protective carrying capacity of the formulations in which water-soluble builders of certain grain size are used with very low surfactant concentration of the same order of magnitude as that of zeolite-containing formulations for color detergents.

Claims (11)

1. Use of water-soluble builders in bleach-free detergents, characterized in that the builder has a particle size distribution that includes particle sizes of 0.4 to 3 mm but excludes particle sizes of 0.2 to less than 0.4 mm.
2. Use according to Claim 1, characterized in that the builder has a particle size distribution of 0.4 to 3 mm.
3. Use according to Claim 1 or 2, characterized in that the water-soluble builder is selected from amorphous alkali metal silicates, sheet silicates, co-granules of silicates with polymeric polycarboxylates, carbonate/silicate compounds and co-granules of sheet silicates/unneutralized polycarboxylates.
4. Use according to one of Claims 1 to 3, characterized in that other builders/co-builders are used together with the water-soluble builder, optionally also as co-granules with the water-soluble builder.
5. Use according to one of Claims 1 to 4, characterized in that the detergent is a light-duty or colour detergent.
6. Bleach-free detergent, characterized in that it contains a water-soluble builder which has a particle size distribution that includes particle sizes of 0.4 to 3 mm but excludes particle sizes of 0.2 to less than 0.4 mm.
7. Detergent according to Claim 6, characterized in that the water-soluble builder has a particle size distribution of 0.4 to 3 mm.
8. Detergent according to Claim 6 or 7, characterized in that the other detergent constituents have a particle size of up to 2500 µm and are present as powder, granules or co-granules.
9. Detergent according to one of Claims 6 to 8, characterized in that it is a light-duty or colour detergent.
10. Detergent according to Claim 9 containing
    15 - 45% of water-soluble builder
    5 - 20% of sodium carbonate
    0 - 15% of sesquicarbonate
    3 - 20% of citrate or citric acid
    3 - 10% of non-ionic surfactant
    3 - 16% of anionic surfactant
    0 - 5% of soap
    0 - 6% of polycarboxylate
    5 - 35% of sulfate
    1 - 10% of additives selected from enzymes, antifoam, oil-solubilizing polymer, carboxymethyl cellulose, perfume, phosphonates and colour bleeding inhibitors.
11. Use of a detergent according to one of Claims 6 to 8 at a wash liquor pH ranging from 8 to 10.