EP0647261B1 - Washing and cleaning granules - Google Patents

Abstract

Washing and cleaning granules which contain anionic or anionic and non-ionic surfactants in amounts comprised between 5 and 45 % by weight and at least one anionic surfactant consisting of sulphurized fatty acid glycerin ester, suffer no losses in washing power, on the contrary of washing and cleaning granules which contain usual surfactants. The alkylbenzolsulphonates can be totally or at least partially substituted, and even ethoxylated fatty alcohols can be at least partially substituted, for example by 10 to 50 % by weight with respect to the amount of non-ionic surfactants, by the anionic surface-active sulphurized fatty acid glycerin esters. Preferred agents contain as further anionic surfactants alkyl sulphate, mixtures of alkyl sulphate and alkylbenzolsulphonate or are free from alkylbenzolsulphonates.

Description

The invention relates to a granular washing and cleaning agent which contains anionic surfactants which are obtained entirely or at least to a large extent from renewable raw materials.

The use of oleochemical surfactant compounds, which are obtained from renewable vegetable and / or animal raw materials and which have high ecological compatibility, is of great and rapidly increasing importance. Examples of such oleochemical surfactant compounds with high environmental compatibility are the known fatty alcohol sulfates, which are produced by sulfating fatty alcohols of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty alcohol molecule and subsequent neutralization to form water-soluble salts, in particular the corresponding alkali metal salts, and the known α-sulfofatty acid alkyl esters (ester sulfonates), which are prepared by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with predominantly 10 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts, in particular the corresponding alkali salts , and their disalts obtainable by hydrolysis.

Examples of further oleochemical surfactant compounds are sulfated fatty acid glycerol esters, for example sulfated unsaturated fatty acid glycerol esters as described in international patent application WO 91/6532, or sulfonation products of saturated fatty acid glycerol esters as described in international patent application WO 91/9009.

The anionic surfactant that is still economically most important today belongs to the surfactant class of alkylbenzenesulfonates. A disadvantage of these alkylbenzenesulfonates is that they are obtained from petrochemical raw materials.

The object was therefore to create a washing and cleaning agent which contains anionic surfactants which either completely or at least form one high proportion consist of native, i.e. renewable, fat chemical raw materials. These anionic surfactants are said to be able to completely or at least partially replace alkylbenzenesulfonates in otherwise customary detergent and cleaning agent formulations without sacrificing washing performance.

The invention accordingly relates to a granular washing and cleaning agent containing anionic or anionic and nonionic surfactants, the surfactant content of the agents being from 5 to 45% by weight and the agents at least one anionic surfactant consisting of sulfonated fatty acid glycerol esters, and contain inorganic image substances selected from zeolites and crystalline layered silicates.

Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production 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. If one starts from fats and oils, that is, natural mixtures of different fatty acid glycerol esters, their fatty acid components usually build up partly from saturated and partly from unsaturated fatty acids. Suitable sulfonated fatty acid glycerol esters are, for example, the sulfonation products of the unsaturated fatty acid glycerol esters which are obtained on the basis of coriander oil, sunflower oil, cottonseed oil, olive oil, peanut oil, linseed oil, fish oil, lard or rape oil rich in oleic acid. The sulfonation can take place in accordance with international patent application W0 91/6532.

However, preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one again starts from fats and oils, i.e. natural mixtures of different fatty acid glycerol esters, it is necessary in this case to largely saturate the starting products with hydrogen in a manner known per se, ie to harden them to iodine numbers less than 5, advantageously less than 2 . Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, or lard oil Lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow. The sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in the international patent application WO 91/9009 is specified.

The sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with an α-position and / or internal sulfonic acid grouping. As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure. In the context of this invention, sulfated fatty acid glycerol esters are understood to mean in each case this complex reaction mixture, including the unsulfated and non-washing-active components, but without aqueous components.

The total surfactant content of the granular washing and cleaning agents is preferably 5 to 40% by weight. The granular agents preferably contain 2 to 25% by weight and in particular 5 to 20% by weight of sulfated fatty acid glycerol esters, sulfated fatty acid glycerol esters with iodine numbers less than 5, in particular less than 2, or mixtures of sulfated fatty acid glycerol esters with iodine numbers less than 5 and sulfated unsaturated fatty acid glycerol esters in a weight ratio of 10: 1 to 1: 1, in particular from 5: 1 to 2: 1, are preferred. Granular agents which contain 0.1 to 5% by weight of sulfated unsaturated fatty acid glycerol esters have a lower foam volume in use than conventional granular agents with conventional surfactants.

Examples of 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, for example, from C ₁₂ -C ₁₈ monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

In the context of this invention, preference is given to mixtures of sulfated fatty acid glycerol esters and the sulfonates mentioned, which consist of 10 to 80% by weight, in particular 10 to 50% by weight, based in each case on the anionic surfactant mixtures, of sulfated fatty acid glycerol esters, the washing power is not significantly impaired compared to the pure sulfonate-containing anionic surfactant mixtures.

The esters of α-sulfofatty acids (ester sulfonates) are also suitable. In particular, esters of α-sulfo fatty acids which are produced by α-sulfonation of the alkyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts are suitable. These are preferably the α-sulfonated esters of hydrogenated coconut, palm kernel or tallow fatty acids, and sulfonation products of unsaturated fatty acids, for example oleic acid, are also present in small amounts, preferably in amounts not above about 2 to 3% by weight could be. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES) are used with particular advantage. Further suitable anionic surfactants are the α-sulfofatty acids obtainable by ester cleavage of the α-sulfofatty acid alkyl esters or their di-salts. The mono-salts of the α-sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts. Mixtures of mono-salts and di-salts with other surfactants, for example with alkylbenzenesulfonate, are also preferred.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol of ethylene oxide, are also suitable. Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm oil and palm kernel oil, which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C ₁₂ , 18 to 30% by weight on C ₁₄ , 5 to 15% by weight on C ₁₆ , are preferred 3% by weight on C ₁₀ and less than 10% by weight on C _{18 are} distributed. The proportion of fatty alkyl sulfates in the granular agents is preferably 2 to 20% by weight and in particular 5 to 15% by weight.

Likewise preferred anionic surfactants are 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 restricted homolog distribution, are particularly preferred.

In addition to the sulfonated fatty acid glycerol esters, preferred granular detergents and cleaning agents contain alkylbenzene sulfonates and / or alkyl sulfate, preferably fatty alkyl sulfate, as further anionic surfactants, the weight ratio of sulfated fatty acid glycerol esters, in particular sulfated fatty acid glycerol esters having iodine numbers less than 5, to alkylbenzenesulfonate and / or alkyl sulfate 1: : 1 and in particular 2: 5 to 2: 1. In particular, granular agents are preferred which do not sulfate alkylbenzenesulfonate, but rather as anionic surfactants Contain fatty acid glycerol esters alone or in a mixture with the other anionic surfactants mentioned. Depending on the recipe, it is even possible for granular detergents and cleaning agents which contain sulfonated fatty acid glycerol esters with iodine numbers less than 5 instead of alkylbenzenesulfonate to achieve the same or better values in terms of washing power than an agent which contains alkylbenzenesulfonate.

Other suitable anionic surfactants are, in particular, soaps, preferably in amounts from 0.2 to 8 and in particular from 0.5 to 5% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The anionic surfactants 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. The anionic surfactants are preferably in the form of their sodium or potassium salts.

In a further preferred embodiment, the granular detergents and cleaning agents also contain nonionic surfactants in addition to the anionic surfactants, preferably in amounts of 1 to 15% by weight and in particular in amounts of 2 to 12% by weight.

The nonionic surfactants used are preferably liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or methyl-branched in the 2-position, or linear and May contain methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. However, linear residues of alcohols of native origin with 12 to 18 carbon atoms, such as, for example, coconut oil, tallow oil or oleyl alcohol, are particularly preferred. In particular, C ₁₂ -C ₁₄ alcohols with 3 E0 or 4 E0, C ₉ -C ₁₁ alcohol 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 5 E0 used.

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 restricted homolog distribution (narrow range ethoxylates, NRE). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.

It was surprising that the anionic surfactant sulfonated fatty acid glycerol esters, especially the sulfonated fatty acid glycerol esters with iodine numbers less than 5, which essentially contain fatty acids with 8 to 22 carbon atoms, can not only at least partially replace other conventional anionic surfactants such as alkylbenzenesulfonate without the washing performance of the detergents being reduced , but that this effect also occurs when in agents with conventional anionic surfactants such as alkylbenzenesulfonate and / or fatty alkyl sulfate, which contain conventional ethoxylated C ₈ -C ₁₈ alcohols as nonionic surfactants, the latter at least partially, for example by 10 to 50% by weight, based on the amount of nonionic surfactant, to be replaced by sulfated fatty acid glycerol esters.

In addition, alkyl glycosides of the general formula R0 (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical branched with methyl in the 2-position with 8 to 22, preferably 12 to 18 C atoms and G denotes the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4. The content of the granular detergents and cleaning agents in alkyl glycosides and in particular in alkyl glucosides is preferably 0.5 to 8% by weight and in particular 1 to 5% by weight.

The granular detergents and cleaning agents according to the invention preferably contain builder substances as further constituents, in particular in amounts of 10 to 65% by weight, it being important to note that they must contain inorganic image substances selected from zeolites and crystalline layered silicates.

Preferred inorganic builder substances are zeolites, crystalline layered silicates and phosphates, provided that the use of phosphates is not objectionable for ecological reasons.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. It 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 C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups . Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water. The zeolite content of the granular agents is preferably 15 to 40% by weight and in particular 20 to 35% by weight (in each case based on anhydrous active substance).

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x 0 _{2x + 1} .yH ₂ 0, 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 are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 164 514. Preferred crystalline layered silicates of the formula are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ 0 are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO91 / 08171.

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), provided that 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 and mixtures of these. The granular detergents and cleaning agents according to the invention preferably contain the polycarboxylates mentioned in amounts of 0.5 to 25% by weight, in particular in amounts of 1 to 20% by weight and with particular advantages in amounts of 5 to 15% by weight , The zeolite content of the agents preferably being about 20 to 35% by weight and in particular about 20 to 32% by weight (in each case based on anhydrous active substance).

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 content of (co) polymeric polycarboxylates in the agents is preferably 1 to 8% by weight.

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 280 223. 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.

Other suitable ingredients of the granular agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous or crystalline silicates or mixtures of these; In particular, alkali carbonate and alkali silicate, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 2 and 15% by weight. The sodium silicate content of the agents is generally up to 10% by weight, preferably between 2 and 8% by weight and in particular 2 to 5% by weight.

The other constituents of the granular agents include bleaching agents and bleach activators, graying inhibitors (dirt carriers), foam inhibitors, optical brighteners, enzymes, textile-softening substances, colorants and fragrances, solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, and neutral salts in the form of sulfates and chlorine their sodium or potassium salts.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.

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 N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. 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.

Graying inhibitors do the job of the fiber. keep loosened dirt suspended in the liquor and thus prevent graying. Water-soluble colloids, mostly of an 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, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances. A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps or, as indicated, by using sulfated unsaturated fatty acid glycerol esters. In the case of soaps, the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin which contain a high proportion of C ₁₈ -C ₂₄ fatty acids are therefore suitable as foam-inhibiting soaps. 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. Mixtures of various foam inhibitors are also advantageously used, for example those made of silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

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.

The salts of polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), are suitable as stabilizers, in particular for per-compounds and enzymes. The salts of the polyphosphonic acids are usually used in amounts of 0.1 to 2.5% by weight, preferably up to 1.5% by weight.

In addition, 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 (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous.

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-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.

It has also been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight. , also contains small amounts, for example 10 ^-6 to 10 ^-3 % by weight, preferably around 10 ^-5 % by weight, of a blue dye. A particularly preferred dye is Tinolux ^(R) (commercial product from Ciba-Geigy).

The granular washing and cleaning agents according to the invention can have a bulk density between about 300 and 1100 g / l. Granules with a bulk density of between 600 and 1100 g / l are preferred.

The granular detergents and cleaning agents can be produced by any of the known processes. For example, it is possible for the granules to be produced by spray drying an aqueous slurry and, if appropriate, then adding temperature-sensitive components. It is also possible for the granular washing and cleaning agents to be produced by one of the known granulating or extruding processes. In a particularly preferred embodiment of the invention, the granules are produced by an extrusion process which is described in international patent application WO 91/2047.

In a further embodiment of the invention, the granular detergents and cleaning agents are produced by using the sulfated fatty acid glycerol esters in the form of a spray-dried or granulated compound as an additive component to other granular constituents of detergents and cleaning agents.

Examples

Production of sulfated saturated fatty acid glycerol esters with iodine numbers less than 5.

In a continuous falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and lateral SO ₃ gassing, about 5 moles of a fatty acid glycerol ester with an iodine number less than 5 (see Table 1) at 80 ° C with about 15 moles of gaseous sulfur trioxide reacted. The fatty acid glycerol ester was sprayed into the reactor through a nozzle with an opening of 0.2 cm in such a way that the starting material formed a continuous fine film with a layer thickness of less than 0.1 cm along the tube wall. The sulfur trioxide was expelled from a corresponding amount of 65% by weight oleum by heating, diluted to a concentration of 2% by volume with nitrogen and blown in at the side of the reactor head. After leaving the sulfonation reactor, the crude sulfonation product was subjected to a post-reaction at 80 ° C. for 30 minutes. The acidic sulfonation product was then continuously neutralized to pH 6.5 to 7.5 using aqueous 25% strength by weight sodium hydroxide solution.

Table 1: Average composition of the fatty acid glycerol esters used after curing, in% by weight fatty acid HK HPK Caproic acid 1 1 Caprylic acid 8th 4th Capric acid 7 5 Lauric acid 48 50 Myristic acid 17th 15 Palmitic acid 9 7 Stearic acid 10th 18th Iodine number 2nd 2nd Legend: HK = hardened coconut oil
HPK = hardened palm kernel oil

Waschprogramm:

Buntwaschprogramm (ohne Vorwäsche) bei 30 °C, 40 °C oder 60 °C

Dosierung:

80 g, 100 g oder 120 g pro Maschine

Wasserhärte:

16 °d

Textilproben:

3,5 kg saubere Füllwäsche (normale Haushaltswäsche)

Bestimmungen:

3fach

Meßtechnische Bedingungen:

künstliche Anschmutzungen:

RFC 3/24 (465 nm, Ausblendung des Aufheller-Effektes)

natürliche Anschmutzungen:

Lange-Gerät (Y-Filter)

Remissionsunterschiede von 2 % und mehr sind als signifikant anzusehen.The following examples describe the tests carried out to test the washing power of the detergents according to the invention in a household washing machine (type: Miele W 717) under the following conditions:

Washing program:

Color wash program (without prewash) at 30 ° C, 40 ° C or 60 ° C

Dosage:

80 g, 100 g or 120 g per machine

Water hardness:

16 ° d

Textile samples:

3.5 kg clean filling laundry (normal household laundry)

Regulations:

3 times

Measurement conditions:

artificial soiling:

RFC 3/24 (465 nm, suppression of the brightener effect)

natural soiling:

Lange device (Y filter)

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

SW-B

Staub-Wollfett auf Baumwolle

SH-B

Staub-Hautfett auf Baumwolle

SH-BV

Staub-Hautfett auf veredelter Baumwolle

SH-P

Staub-Hautfett auf Polyester

SH-PBV

Staub-Hautfett auf einem Gemisch aus Polyester und veredelter Baumwolle

R-BV

Rotwein auf veredelter Baumwolle

T-BV

Tee auf veredelter Baumwolle

MU-PBV

Make-up auf einem Gemisch aus Polyester und veredelter Baumwolle

The stains were:

SW-B

Dust-wool grease on cotton

SH-B

Dust skin fat on cotton

SH-BV

Dust-skin fat on refined cotton

SH-P

Dust skin grease on polyester

SH-PBV

Dusty skin fat on a mixture of polyester and refined cotton

R-BV

Red wine on refined cotton

T-BV

Tea on refined cotton

MU-PBV

Make-up on a mixture of polyester and refined cotton

The compositions of the basic agents W1 and W2 were (data in% by weight):

The agents consisted of spray-dried granules, which were sprayed with ethoxylated C ₁₂ -C ₁₈ fatty alcohol and to which the temperature-sensitive components had been subsequently mixed. The bulk density was 650 g / l or 670 g / l.

W1/V , W2/V

C₉-C₁₃-Alkylbenzolsulfonat, Natriumsalz

W1/1 , W2/1

sulfiertes HK

W1/2 , W2/2

sulfiertes HPK

W1/3

Mischung aus sulfiertem HK und Talgfettalkoholsulfat in einem Gewichtsverhältnis von 1 : 1

W1/4

Mischung aus sulfiertem HPK und Talgfettalkoholsulfat in einem Gewichtsverhältnis von 1 : 1

The following were used as "anionic surfactants":

W1 / V, W2 / V

C ₉ -C ₁₃ alkylbenzenesulfonate, sodium salt

W1 / 1, W2 / 1

sulfated HK

W1 / 2, W2 / 2

sulfated HPK

W1 / 3

Mixture of sulfated HK and tallow fatty alcohol sulfate in a weight ratio of 1: 1

W1 / 4

Mixture of sulfated HPK and tallow fatty alcohol sulfate in a weight ratio of 1: 1

Example 1: Testing W1, dosage 80 g

The experiments were carried out at 30 ° C (Table 2), 40 ° C (Table 3), and 60 ° C (Table 4). Table 2: T = 30 ° C medium % Remission on soiling SW-B T-BV MU-BV W1 / V 70.5 59.6 69.8 W1 / 3 69.8 59.3 69.9 W1 / 4 70.2 58.8 69.4 T = 40 ° C medium % Remission on soiling SW-B SH-BV SH-PBV SH-P R-BV T-BV MU-PBV W1 / V 71.6 77.4 69.7 74.6 54.1 63.7 70.4 W1 / 1 70.7 78.6 68.6 75.9 54.1 --- 70.3 W1 / 2 69.9 79.1 68.1 --- --- --- 70.8 W1 / 3 72.8 78.9 68.6 75.8 54.9 63.8 71.3 W1 / 4 72.1 79.1 70.3 74.4 54.3 63.9 73.7 T = 60 ° C medium % Remission on soiling SW-B SH-BV SH-PBV SH-P R-BV T-BV MU-PBV W1 / V 75.6 80.8 70.1 77.1 60.2 68.3 72.7 W1 / 1 76.7 81.5 73.9 76.8 63.7 72.1 74.4 W1 / 2 76.4 80.8 71.7 --- 62.8 70.6 75.9 W1 / 3 76.9 79.7 72.6 77.1 64.8 71.8 74.7 W1 / 4 76.1 79.3 72.7 --- 64.9 71.3 74.8

Example 2: Testing W1, dosage 120 g

The experiments were repeated in accordance with Example 1. Table 5: T = 30 ° C medium % Remission when soiled SH-PBV W1 / V 69.8 W1 / 1 69.2 W1 / 3 68.9 T = 40 ° C medium % Remission when soiled SH-BV SH-PBV SH-P R-BV T-BV MU-PBV W1 / V 80.9 72.6 76.1 54.9 65.6 72.9 W1 / 1 82.4 74.7 76.2 58.6 67.3 73.9 W1 / 2 79.3 --- --- 53.7 --- 71.9 W1 / 3 81.7 73.3 --- 58.4 67.1 73.6 W1 / 4 81.3 72.6 --- 58.2 67.8 74.7 T = 60 ° C medium % Remission when soiled SW-B SH-BV SH-PBV SH-P MU-PBV W1 / V 77.9 83.4 75.1 77.3 75.8 W1 / 1 80.6 84.1 77.2 76.9 76.8 W1 / 2 78.4 83.6 74.7 75.6 76.1 W1 / 3 78.4 82.8 --- --- 75.2 W1 / 4 78.6 82.8 --- --- 76.1

Example 3: Testing W2

The results of the tests at 40 ° C and a dosage of 100 g are summarized in Table 8. Table 8: medium % Remission when soiled SW-B SH-B SH-PBV SH-P R-BV T-BV MU-PBV W2 / V 56.0 67.1 66.7 72.8 55.7 65.1 65.5 W2 / 1 56.7 67.3 65.9 72.5 53.9 64.4 63.8 W2 / 2 58.1 --- --- --- 54.7 65.9 64.1

Claims (14)

1. A granular detergent containing anionic or anionic and nonionic surfactants, characterized in that the surfactant content of the detergent is 5 to 45% by weight, the detergent containing at least one anionic surfactant consisting of sulfonated fatty acid glycerol esters and inorganic builders selected from zeolites and crystalline layer silicates.
2. A granular detergent as claimed in claim 1, characterized in that it contains sulfonated fatty acid glycerol esters obtained from fatty acid glycerol esters with iodine values below 5, preferably from mono-, di- and triglycerides or mixtures thereof with iodine values below 5 which contain C_6-22 fatty acids, by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases.
3. A granular detergent as claimed in claim 1 or 2, characterized in that the surfactant content of the detergent is 5 to 40% by weight and the builder content 10 to 65% by weight, the detergent containing 2 to 25% by weight of sulfonated fatty acid glycerol esters, 1 to 15% by weight of nonionic surfactants and zeolite as builder.
4. A granular detergent as claimed in any of claims 1 to 3, characterized in that ethoxylated fatty alcohols and/or alkyl glycosides are used as nonionic surfactants, the content of sulfonated fatty acid glycerol esters in the detergent preferably being 5 to 20% by weight and the content of nonionic surfactants preferably being 2 to 12% by weight.
5. A granular detergent as claimed in any of claims 1 to 4, characterized in that it contains other anionic surfactants from the group of sulfonates, sulfates and soaps.
6. A granular detergent as claimed in claim 5, characterized in that it contains alkyl benzenesulfonate and/or alkyl sulfate, preferably fatty alkyl sulfate, as further anionic surfactants, the ratio by weight of sulfonated fatty acid glycerol ester to alkyl benzenesulfonate and/or alkyl sulfate being 1:9 to 4:1 and, more particularly, 2:5 to 2:1.
7. A granular detergent as claimed in claim 1 or 6, characterized in that it is free from alkyl benzenesulfonates.
8. A granular detergent as claimed in any of claims 1 to 7, characterized in that it has a zeolite content of 15 to 40% by weight (based on anhydrous active substance).
9. A granular detergent as claimed in any of claims 1 to 8, characterized in that it contains polycarboxylates, preferably citrate, succinate, tartrate, glutarate, adipate or mixtures thereof in quantities of 0.5 to 25% by weight, preferably 1 to 20% by weight and more preferably 5 to 15% by weight as organic builders.
10. A granular detergent as claimed in any of claims 1 to 9, characterized in that it contains a mixture of sulfonated fatty acid glycerol esters with iodine values below 5 and sulfonated unsaturated fatty acid glycerol esters in a ratio by weight of 10:1 to 1:1 and preferably 5:1 to 2:1.
11. A granular detergent as claimed in any of claims 1 to 10, characterized in that it has an apparent density of 600 to 1,100 g/l.
12. A process for the production of the granular detergent claimed in any of claims 1 to 11, characterized in that the granules are produced by spray drying.
13. A process for the production of the granular detergent claimed in any of claims 1 to 11, characterized in that the granules are produced by a granulation or extrusion process.
14. A process for the production of the granular detergent claimed in any of claims 1 to 11, characterized in that the sulfonated fatty acid glycerol esters are used in the form of a spray-dried or granulated compound designed for mixing with other granular constituents of detergents.