WO1999010471A1 - Solid detergents containing fatty acid polyglycol ester sulphates and solid builders - Google Patents

Abstract

The invention relates to solid detergents in the form of powders or granules, containing a) fatty acid polyglycol ester sulphates and b) solid builders. The inventive products are characterised in that they are especially pourable and have excellent technological application properties.

Description

SOLID DETERGENT CONTAINING FATTY ACID POLYGLYCOLESTER SULFATES AND SOLID BUILDER

Field of the Invention

The invention is in the field of solid detergents and relates to free-flowing preparations in the form of powders or granules with a high bulk density containing selected anionic surfactants and builders and the use of the anionic surfactants for the preparation of the compositions.

State of the art

Modern detergents, which are commercially available in the form of conventional powders or granules, usually contain a high proportion of anionic surfactants, such as, for example, alkyl benzene sulfonates or alkyl sulfates. Although these are characterized by a high washing capacity, they have the disadvantage that they crystallize only with difficulty and show a high tendency to take up water from the air and then to clump together. Remedial measures are taken, for example, by "powdering" the anionic surfactants, i.e. by coating them with silica, in order to make it more difficult for water to enter. It is obvious that such post-treatment of raw materials or end products represents an additional technical measure which makes the sales product more expensive.

Accordingly, the complex object of the invention was to provide solid detergents in the form of powders or granules which avoid the disadvantages described and which, in particular, have a high anionic surfactant content, but which are free-flowing even after prolonged storage, have a high bulk density, have an optimal cleaning performance over the largest possible range of impurities and also cause the smallest possible incrustations. Description of the invention

The invention relates to solid detergents in the form of powders or granules, which are characterized in that they

(a) fatty acid polyglycol ester sulfates and

(b) solid builders

contain.

Surprisingly, it has been found that the preparations have a comparatively low tendency to clump, are extremely free-flowing, have a high bulk density and, moreover, have excellent cleaning properties against a large number of very different types of soiling. Another advantage is that the agents cause relatively little incrustation. The invention includes the knowledge that the application properties of the powder detergents can be further improved if the fatty acid polyglycol ester sulfates are mixed with other surfactants. The preferred co-surfactants are - in addition to alkali soaps - alkylbenzenesulfonates, alkyl sulfates, alkyl oligoglucosides, alcohol ethoxylates and again their mixtures.

Fatty acid repol yg I ycolestersulfate

Fatty acid polyglycol ester sulfates, which form component (a) and follow formula (I),

R ¹ COO (AO) _x S0 ₃ X (I)

in the R ¹ CO for a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, x for numbers from 1 to 3 on average and AO for a CH2CH2O-, CH CH (CH ₃ ) 0- and / or CH (CH ₃ ) CH ₂ 0 radical and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium are prepared by sulfating the corresponding fatty acid polyglycol esters. These in turn can be obtained using the relevant preparative processes in organic chemistry. For this purpose, ethylene oxide, propylene oxide or a mixture thereof - in random or block distribution - is added to the corresponding fatty acids, this reaction being acid-catalyzed, but preferably in the presence of bases, such as sodium methylate or calcined hydrotalcite. If a degree of alkoxylation of 1 is desired, the intermediates can also be prepared by esterifying the fatty acids with an appropriate alkylene glycol. The sulfation of the fatty acid polyglycol esters can be carried out in a manner known per se Chlorosulfonic acid or preferably gaseous sulfur trioxide are carried out, the molar ratio between fatty acid polyglycol ester and sulfating agent in the range from 1: 0.95 to 1: 1, 2, preferably 1: 1 to 1: 1, 1 and the reaction temperature 30 to 80 and preferably 50 can be up to 60 ° C. It is also possible to undersulfate the fatty acid polyglycol esters, ie to use significantly fewer sulfating agents than would be stoichiometrically required for complete conversion. For example, if one chooses molar amounts of fatty acid polyglycol ester to sulfating agent from 1: 0.5 to 1: 0.95, mixtures of fatty acid polyglycol ester sulfates and fatty acid polyglycol esters are obtained, which are also advantageous for a whole range of applications. In order to avoid hydrolysis, it is very important to carry out the neutralization at a pH in the range from 5 to 9, preferably 7 to 8. Typical examples of suitable starting materials are the addition products of 1 to 3 moles of ethylene oxide and / or propylene oxide, but preferably the adducts with 1 mole of ethylene oxide or 1 mole of propylene oxide with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, Palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, which are then sulfated and neutralized as described above. Fatty acid polyglycol ester sulfates of the formula (I) are preferably used in which R ¹ CO stands for an acyl radical having 12 to 18 carbon atoms, x for an average of 1 or 2, AO for a CH2CH2θ group and X for sodium or ammonium, such as lauric acid + 1 EO sulfate sodium salt, lauric acid + 1 EO sulfate ammonium salt, coconut fatty acid + 1 EO sulfate sodium salt, coconut fatty acid + 1 EO sulfate ammonium salt, tallow fatty acid + 1 EO sulfate sodium salt, tallow fatty acid + 1 EO sulfate Ammonium salt and mixtures thereof. In the simplest case, the proportion of fatty acid polyglycol ester sulfates in the powder detergents makes up 100% by weight of the surfactant component and can then be in the range from 5 to 50, preferably 10 to 40 and in particular 15 to 25% by weight, based on the powder detergent.

Fixed builders

In particular, fine crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality is used as the solid builder substance. However, zeolite NaX and mixtures of NaA and NaX are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. 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% by weight, based on zeolite, of ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated Isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (vol. distribution of spaces; Measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.

Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSixC yH∑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. Such crystalline layered silicates are described, for example, in European patent application EP-A 0164514. Preferred crystalline layered silicates are those in which M in the general formula stands for sodium and x assumes the values 2 or 3. In particular, both ß- and γ-

Sodium disilicate Na2Si ₂ θ5-yH2θ is preferred, wherein β-sodium disilicate can be obtained, for example, by the process described in international patent application WO 91/08171. The powder detergents according to the invention preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous. In particular, it is preferred that the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates. Particularly preferred agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance. Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates. Particularly preferred are agents which contain, in particular, sodium silicate with a molar ratio (module) Na0O: Si0 ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5. The content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight. Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions. The content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight. Layered silicates of this type are known, for example, from patent applications DE-B 2334899, EP-A 0026529 and DE-A 3526405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas

(OH) 4Si8-yAl _y (Mg _x Al4-x) 0 ₂ o Montmorrilonit (CΗ) 4Si.-yAly (Mg6-zLiz) θ2o Hectorite (OH) 4Si ₈ -yAl _y (Mg6-z Al _z ) 0 ₂ o Saponite

with x = 0 to 4, y = 0 to 2, z = 0 to 6. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, because of their ion-exchanging properties, the layered silicates can hydrogen, alkali, alkaline earth ions, in particular Contain Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP-A 0026529 and EP-A 0028432. Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), 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. Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid). Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The use of polymeric polycarboxylates is not absolutely necessary. However, if polymeric polycarboxylates are used, agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives or the monomers acrylic acid and 2-alkylallylsulfonic acid or salts thereof as well as sugar derivatives. Terpolymers which are obtained according to the teaching of German patent applications DE-A 4221381 and DE-A 4300772 are particularly preferred.

Further 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 0280223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Co-surfactants

In addition to the fatty acid polyglycol ester sulfates, the powder detergents can contain further anionic and / or nonionic co-surfactants. Typical examples of anionic surfactants are soaps, alkyl benzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether, α-methyl ester sulfonates, sulfofatty acids mischethersulfate, alkyl sulfates, fatty alcohol ether sulfates, Glycerol ether, hydroxy, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and Dialkylsulfo- succinate, mono- and sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, protein fatty acid condensates (in particular vegetable products based on wheat) and alkyl (ether) phosphates . If the anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, optionally partially oxidized alk (en) yl oligoglycosides or especially glucoronic acid-protein hydrolysis products, fatty acid glucoramide acid, vegetable glucose acids, vegetable glucose acids, vegetable glucoramide acid derivatives, and vegetable glycate acid derivatives Wheat base), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrowed, homogeneous distribution. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example, J.Falbe (ed.), "Sur-factants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), " Catalysts, surfactants and mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp. 123-217. The proportion of co-surfactants in the surfactant component of the powder detergents according to the invention can make up 10 to 90, preferably 25 to 75 and in particular 40 to 60% by weight.

Alkylbenzenesulfonates

Alkylbenzenesulfonates which are suitable as preferred anionic cosurfactants preferably follow the formula (II),

R2-Ph-S0 ₃ X (II)

in which R ^{2 is} a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably used. Alkyl and / or alkenyl sulfates

Alkyl and / or alkenyl sulfates, which are also referred to as fatty alcohol or oxo alcohol sulfates depending on the raw material base and are another preferred anionic co-surfactant, are the sulfation products of primary alcohols which follow the formula (III),

R ³ 0-S0 ₃ X (III)

in which R ^{3 represents} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Typical examples of alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palm oleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, arachselyl alcohol, elaidyl alcohol, elaidyl alcohol alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on Ci6 / 18 tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred.

Alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides, which are preferred nonionic cosurfactants, preferably follow the formula (IV),

R ⁴ 0- [G] _p (IV)

in which R ^{4 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B.Salka in Cosm.Toil. 108, 89 (1993) and J.Kahre et al. in SÖFW-Journal Issue 8, 598 (1995).

The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (IV) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁴ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Preferred are alkyl oligoglucosides of chain length C ₈ -Cι ₀ (DP = 1 to 3), which are obtained as a preliminary step in the separation of technical C ₈ -Ci8 coconut fatty alcohol by distillation and with a proportion of less than 6% by weight of C12- Alcohol can be contaminated as well as alkyl oligoglucosides based on technical Cg / n-oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁴ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as well as their technical mixtures. Alkyl oligoglucosides based on hydrogenated Ci2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.

Alcohol ethoxylates

A further group of preferred nonionic co-surfactants are alcohol ethoxylates, which are referred to as fatty alcohol or oxo alcohol ethoxylates for production reasons and preferably follow the formula (V),

in which R ^{5 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n represents numbers from 1 to 50. Typical examples are the adducts of on average 1 to 50, preferably 5 to 40 and in particular 10 to 25 moles of capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol Arachyl Petroselinyl Alcohol alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, which are obtained, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols. Adducts of 10 to 40 moles of ethylene oxide with technical fatty alcohols with 12 to 18 carbon atoms, such as, for example, coconut, palm, palm kernel or tallow fatty alcohol, are preferred.

The powder detergents according to the invention can contain the fatty acid polyglycol ester sulfates and the cosurfactants in a weight ratio of 10:90 to 90:10, preferably 25:75 to 75:25 and in particular 40:60 to 60:40. Mixtures of anionic and nonionic cosurfactants, in particular alkyl sulfates with alkyl oligoglucosides or fatty alcohol ethoxylates, have proven to be particularly advantageous.

Industrial applicability

A particular advantage of the fatty acid polyglycol ester sulfates is that they crystallize very easily from aqueous solutions or pastes and their tendency to add water and then clump together is extremely low. These anionic surfactants can therefore be processed in a special way to free-flowing powders with a high bulk density. Taking their excellent stain-removing properties into account, another object of the invention therefore relates to the use of fatty acid polyglycol ester sulfates, alone or in admixture with anionic and / or nonionic surfactants for the production of powder detergents.

Powder detergent

In addition to the surfactants and builders mentioned, the powder detergents can also contain other typical ingredients, such as bleaching agents, bleach activators, detergent boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repellants, foam inhibitors, inorganic salts and fragrances and colorants.

Among the compounds which serve as bleaching agents and which supply hydrogen peroxide in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Because of its ability to Being able to bind free water to the formation of the tetrahydrate helps to increase the stability of the agent.

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 hydrogen peroxide, preferably N.N'-tetraacyated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate. 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'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phosphonates, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.

Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferred. As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, 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 which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example 10- ⁶ to 10 ^"3 wt .-%, preferably 10- ⁵ wt .-% of a blue dye. a particularly preferred dye is contained Tinolux® (commercial product of Ciba-Geigy).

Suitable soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100. The polymers are characterized by an average molecular weight of approximately 5000 to 200,000 and can have a block, but preferably a random structure Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight have from 750 to 5000, preferably from 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Soaps of natural or synthetic origin with a high content of Ci8-C24 fatty acids are suitable. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

n Manufacturing process

The bulk density of the detergents is generally 300 to 1200 g / l, in particular 500 to 1100 g / l. They can be produced by any of the known processes such as mixing, spray drying, granulating and extruding. Processes in which several partial components, for example spray-dried components and granulated and / or extruded components, are mixed with one another are particularly suitable. It is also possible for spray-dried or granulated components to be subsequently treated, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes. In granulation and extrusion processes in particular, it is preferred to use the anionic surfactants in the form of a spray-dried, granulated or extruded compound either as an additive component in the process or as an additive to other granules. In particular, the preferred heavier granules with bulk densities above 600 g / l preferably contain components which improve the flushing behavior and / or the dissolving behavior of the granules. Alkoxylated fatty alcohols with 12 to 80 moles of ethylene oxide per mole of alcohol, for example tallow fatty alcohol with 14 EO, 30 EO or 40 EO, and polyethylene glycols with a relative molecular weight between 200 and 12000, preferably between 200 and 600, are advantageously used for this purpose.

It is also possible and, depending on the recipe, to be advantageous if additional individual constituents of the agent, for example citrate or citric acid or other polycarboxylates or polycarboxylic acids, polymeric polycarboxylates, zeolite and / or layered silicates, which can optionally be crystalline, subsequently to spray-dried, granulated and / or extruded components, which may have nonionic surfactants and / or other ingredients which are liquid to waxy at the processing temperature, mixed. A method is preferred in which the surface of partial components of the composition or of the entire composition is subsequently treated to reduce the stickiness of the granules rich in nonionic surfactants and / or to improve their solubility. Suitable surface modifiers are known from the prior art. In addition to other suitable, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts, for example calcium stearate, but especially mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred. Examples

Granular detergents of the following composition were prepared in a conventional manner by spray drying. The components perborate, bleach activator, enzyme granulate and defoamer granulate were subsequently mixed in. The primary and secondary washing capacity was checked in a household washing machine (type Miele W 717). For this purpose, the machines were loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric, the test fabric for testing the primary washing ability was partially impregnated with conventional test soiling and for testing the secondary washing ability partially consisted of white fabric. Strips of standardized cotton fabric (Krefeld laundry research institute; WFK), nettle (BN), knitwear (cotton jersey; B) and terry toweling fabric (FT) were used as the white test fabric.

Washing conditions

Washing program: Cottons without prewash at 90 ° C (heating up time 60 min, 15 min at 90 ° C)

Dosage: 98 g per machine

Water hardness: 23 ° d

Liquor ratio: 1: 5.7 (kg of laundry: liters of wash water in the main wash cycle),

Rinse 4 times with tap water, spin off and dry

Measurement conditions

• artificial soiling: RFC3 / 24 (465nm, suppression of the brightening effect)

• natural soiling: length device (Y filter)

• Differences in remission of 2% and more can be regarded as significant.

Soiling used:

SW-B: Dust-wool grease on cotton

SH-B: Dust-skin fat on cotton

SH-BV: Dust-skin fat on refined cotton

SH-PBV: Dust-skin grease on a mixture of polyester and refined cotton

LS-PBV: lipstick on a mixture of polyester and finished cotton

MU-PBV: Make-up on a mixture of polyester and finished cotton The ash content of the textile samples and the total incrustation were determined as follows after 25 washing cycles:

1. Weighing the untreated tissue,

2. Weighing of the fabric after 25 washing cycles),

3. Weighing of the tissue after extraction with EDTA,

4. Determination of the so-called "soluble ash" from the difference between the weighings 2 and 3,

5. ashing of the extracted tissue to determine the residual ash,

6. Determination of the total incrustation from the sum of the soluble ash and the residual ash.

The results are summarized in Table 1. Preparations 1 to 5 are according to the invention; the powder detergent V1 is used for comparison. All quantities are understood as% by weight.

Table 1 Powder detergent

*) Sokalan CP5

Claims

claims 1. Solid detergent in the form of powders or granules, characterized in that they (a) fatty acid polyglycol ester sulfates and (b) solid builders contain. 2. Composition according to claim 1, characterized in that they contain fatty acid polyglycol ester sulfates of the formula (I), R ¹ COO (AO) _x S0 ₃ X (I) in which R ¹ CO is a linear or branched, saturated or unsaturated acyl radical having 6 to 22 carbon atoms, x is an average of 1 to 3 and AO is a CH2CH2O-, CH ₂ CH (CH ₃ ) 0- and / or CH ( CH ₃ ) CH ₂ 0 radical and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. according to claims 1 or 2, characterized in that they contain solid builders selected from the group consisting of zeolites, layered silicates and polycarboxylic acids. according to at least one of claims 1 to 3, characterized in that they contain anionic cosurfactants which are selected from the group consisting of soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfofatty acids , Alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide acid ethersates, salzenic acid sulfates, fatty acid sulfates, ether carboxylic acid sulfates, ether carboxides, , Fatty acid taurides, N-acylamino acids, alkyl oligoglucoside sulfates, protein fatty acid condensates and alkyl (ether) phosphates. Agents according to at least one of claims 1 to 4, characterized in that they contain nonionic co-surfactants which are selected from the group consisting of fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formal, optionally partially oxidized alk (en) yl oligoglycosides or glucoronic acid derivatives, fatty acid N-alkyl glucamides, protein hydrolyzates, polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. 6. Composition according to at least one of claims 1 to 5, characterized in that they contain alkylbenzenesulfonates of the formula (II) as anionic cosurfactants, R2-Ph-S0 ₃ X (II) X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. 7. Compositions according to at least one of claims 1 to 6, characterized in that they contain alkyl and / or alkenyl sulfates of the formula (III) as anionic co-surfactants, R30-S0 ₃ X (III) in which R ^{1 is} a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. 8. Composition according to at least one of claims 1 to 7, characterized in that they contain alkyl and / or alkenyl oligoglycosides of the formula (IV) as nonionic co-surfactants, R ⁴ 0- [G] _P (IV) in which R ^{1 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. 9. Composition according to at least one of claims 1 to 8, characterized in that they contain alcohol ethoxylates of the formula (V) as nonionic co-surfactants, R ⁵ 0 (CH ₂ CH ₂ 0) _n H (V) in which R ^{5 represents} a linear or branched alkyl and / or alkenyl radical having 6 to 22 carbon atoms and n represents numbers from 1 to 50. Use of fatty acid polyglycol ester sulfates, alone or in a mixture with anionic and / or nonionic co-surfactants, for the production of solid detergents in the form of powder or granules.