EP0966510B1 - Process for making granular secondary alkane sulphonate - Google Patents

Description

Secondary alkane sulfonates (SAS) have been an important one for many years Product group within the anionic surfactants. Secondary alkane sulfonate in solid Form, however, has the undesirable property of being hygroscopic. Due to this property, solid SAS is only used as pellets or flakes in the Brought to trade. The hygroscopic quality of the SAS doesn't matter. For the production of powdery, homogeneous washing and Cleaning agents, however, it is necessary that all components in finely divided form available. Fine-particle SAS agglomerates due to its hygroscopic Property, so that such powder detergents and cleaning agents with a SAS content does not remain in the finely divided form. The use of SAS is therefore essentially limited to liquid detergents and cleaning agents.

In the past there has been no lack of attempts to use sec. To enable alkanesulfonates also in solid washing and cleaning agents.

For example, DE-A-2 415 159 describes a product which can be spray dried an aqueous solution of alkanesulfonate and a carrier material is obtained. Inorganic salts are essentially suitable as carrier material. The The amount of these salts is quite high and is 50 to 95% by weight based on the total amount of alkanesulfonate and carrier material.

WO 93/16164 describes the preparation of anionic surfactant salts by a Spray neutralization, in which the anionic surfactants in their acid form together with aqueous solutions of bases are sprayed. Suitable ones can be used here dust-binding auxiliaries are added.

Mixtures of alkanesulfonate and zeolites are known from JP 89-142 999. DE-A 2 745 691 describes SAS in powder form, the SAS having no additive or Contains anti-caking agents.

JP-A-1 229 100 describes mixtures of alkanesulfonate and silica. EP-A-688 861 describes granules of alkanesulfonate and silica and EP-A-30 859 mixtures of alkanesulfonate, tripolyphosphate and silicate.

The present invention is based, solid SAS in finely divided the task Form to provide that directly as a surfactant component in powder form Detergents and cleaning agents can be incorporated homogeneously without it here agglomerates are formed or in the usual way together with components common in detergents and cleaning agents Extrudates, compacts or compacts can be processed further.

The invention relates to a method for producing a powdered or granular secondary alkanesulfonate with a grain size of 0.1 to 3 mm, by grinding solid secondary alkanesulfonate in the presence of 0.1 to 10 wt .-%, based on the Amount of secondary alkanesulfonate, a non-hygroscopic additive.

Solid sec. Serves as the starting material. Alkanesulfonate, for example in the form of Pellets (Hostapur® SAS 93) or in the form of flakes. In this secondary Alkanesulfonate can branch the alkyl group either saturated or unsaturated or linear and optionally substituted with a hydroxyl group. The Sulfo group can be at any position on the C chain, the primary Methyl groups at the beginning and end of the chain have no sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains with approx. 9-25 carbon atoms, preferably 10 to 20, and particularly preferably approx. 13 to 17 Carbon atoms. The cation is, for example, sodium, potassium, ammonium, Mono-, di- or triethanolammonium, calcium or magnesium and mixtures from that. Sodium as the cation is preferred

The alkanesulfonate is prepared according to the invention by grinding SAS in the form of pellets or flakes, as is usually the case in production from fixed SAS. In a first embodiment, this is rough SAS mixed intensively with the additive before grinding and then ground. In principle, all grinding devices, such as. B. impact mills, Cutting mills, roller mills or air jet mills. Impact mills are for example beater wheel mills with and without internals, pin mills and Disintegrators especially with ground pins, universal mills with various work organs, especially with hammer-like work organs. Cutting mills, universal mills with a cross and are particularly preferred Impact plate mills with strainer basket and cross beater / turbine (e.g. Pralitell mills from Type PP / PPS from Pallmann).

Alternatively, one can also use a premix of alkanesulfonate and Dispense with the additive and the additive simultaneously with the alkanesulfonate give the grinder. Coarser materials can also be used with one Diameters in the millimeter range can be used as they are used for grinding crushed itself and intensively with the mechanical action Alkanesulfonate are mixed.

The mixture of alkanesulfonate and additive can be ground with cooling done to dissipate the frictional heat and the shredding process through to support cold embrittlement. To do this, either the mill can directly be cooled or you cool the airflow drawn in by the mill if it is is a continuous grinding process. You can also see the sec. Pre-cool the alkanesulfonate or use a refrigerant such as Add dry ice as an example. With this shredding process, this is the case make sure that the entry of moisture, especially the humidity after the Grinding (until the product temperature matches the Ambient temperature) e.g. is avoided by equipment measures.

In all of the described process variants, the SAS and, if necessary, also the additive to a grain size of 0.1 to 3, preferably 0.5 to 2 mm ground.

A large number of compounds come as additives in the context of this invention in question. They can be water-soluble, but they are preferred hydrophobic. In any case, the prerequisite is that these additives are not hygroscopic are. Additives that are already preferred from the outset are also preferred finely divided form.

Suitable additives are, for example, long-chain fatty acids, in particular C ₁₈ -C ₂₂ fatty acids, such as stearic acid and behenic acid, their salts, in particular the alkaline earth metal salts, fatty alcohols, polymers such as high molecular weight polyethylene glycols, for example PEG 20,000, polyacrylates, for example ®Sokalan CP 5, cellulose and their derivatives such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, waxes, for example montan waxes, paraffin waxes, ester waxes, polyolefin waxes, bentonites, for example ®Laundrosil DGA from Südchemie, magnesium oxide, chalk, kaolin, magnesium silicate, silica chalk, diatomaceous earth, silica or alkaline earth metal, alkali metal sulfate , The preferred additives include synthetic, finely divided, highly disperse silicas, for example pyrogenic silicas (®Aerosil brands from Degussa) and precipitated silicas, for example the commercial products ®Sident 12, Sident 12 DS, FK 160, FK 300 DS, FK 310, FK 320, FK 320 DS, FK 383 DS, FK 500 LS, FK 700, ®Sipernat 22, Sipemat 22S, Sipernat 30, Sipemat 50, Sipemat 50 S, Sipemat D 17, ®Ultrasil VN 2, Ultrasil VN 3, ®Wessalon and Wessalon S from Degussa. Such silicas are naturally hydrophilic, but it is also possible to use hydrophobically modified silicas, such as Sipernat D 17 or Aerosil R 972.

The aforementioned additives are used in a concentration of 0.1 to 10%, preferably 0.5 to 5% and particularly preferably 0.5 to 2%, based on sec. Alkanesulfonate used.

The powdery or granular sec. Alkane sulfonate can be directly incorporated into detergents and cleaning agents as a surfactant component. Such powder detergents and cleaning agents can be, for example, washing powder, stain salts, abrasives and other solid mixtures.
Another possibility is to process the powdery or granular SAS according to the invention into solid extrudates such as, for example, wash pieces, bar soaps or toilet blocks, into compacts, for example tablets, or compactates (rollers).

The sec. Alkanesulfonate can be used in the finished washing and Detergent formulations either alone or in combination with others Surfactants are used.

The total concentration of surfactants including the sec. Alkanesulfonate can be from 1% to 99%, preferably between 5% and 80% are particularly preferably between 5% and 40%.

The following surfactants can, for example, together with the invention granular secondary alkanesulfonate combined in detergents and cleaning agents become.

Suitable anionic surfactants are sulfates, sulfonates, carboxylates, phosphates and mixtures thereof. Suitable cations are alkali metals, such as. B. sodium or potassium or alkaline earth metals, such as. As calcium or magnesium and ammonium, substituted ammonium compounds, including mono-, di- or triethanolammonium cations, and mixtures thereof. The following types of anionic surfactants are of particular interest:
Alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, olefin sulfonates and soaps as described below.

worin R¹ einen C₈-C₂₀-Kohlenwasserstoffrest, bevorzugt Alkyl, und R einen C₁-C₆ Kohlenwasserstoffrest, bevorzugt Alkyl, darstellt. M steht für ein Kation, das ein wasserlösliches Salz mit dem Alkylestersulfonat bildet. Geeignete Kationen sind Natrium, Kalium, Lithium oder Ammoniumkationen, wie Monoethanolamin, Diethanolamin und Triethanolamin. Bevorzugt bedeuten R¹ C₁₀-C₁₆-Alkyl und R Methyl, Ethyl oder Isopropyl. Besonders bevorzugt sind Methylestersulfonate, in denen R¹ C₁₀-C₁₆-Alkyl bedeutet.Alkyl ester sulfonates include linear esters of C ₈ -C ₂₀ carboxylic acids (ie fatty acids) which are sulfonated using gaseous SO ₃ , as described in "The Journal of the American Oil Chemists Society" 52 (1975), pp. 323-329. Suitable starting materials are natural fats such as tallow, coconut oil and palm oil, but can also be synthetic in nature. Preferred alkyl ester sulfonates, especially for detergent applications, are compounds of the formula

wherein R ^{1 is} a C ₈ -C ₂₀ hydrocarbon radical, preferably alkyl, and R is a C ₁ -C ₆ hydrocarbon radical, preferably alkyl. M stands for a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable cations are sodium, potassium, lithium or ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. R ^{1 is} preferably C ₁₀ -C ₁₆ alkyl and R is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R ^{1 is} C ₁₀ -C ₁₆ alkyl are particularly preferred.

Here, alkyl sulfates are water-soluble salts or acids of the formula ROSO ₃ M, in which R is a C ₁₀ -C ₂₄ hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical with a C ₁₀ -C ₂₀ alkyl component, particularly preferably a C ₁₂ -C ₁₈ alkyl or Is hydroxyalkyl. M is hydrogen or a cation, e.g. an alkali metal cation (e.g. sodium, potassium, lithium) or ammonium or substituted ammonium, e.g. B. methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Alkyl chains with C ₁₂ -C ₁₆ are preferred for low washing temperatures (e.g. below approx. 50 ° C) and alkyl chains with C ₁₆ -C ₁₈ for higher washing temperatures (e.g. above approx. 50 ° C).

Alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) _m SO ₃ M,
wherein R represents an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl radical, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl radical, particularly preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy unit, m is a number greater than 0, preferably between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as, for , As sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation. Specific examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine or mixtures thereof. Examples include C ₁₂ to C ₁₈ fatty alcohol ether sulfates, the content of EO being 1, 2, 2.5, 3 or 4 mol per mol of the fatty alcohol ether sulfate, and in which M is sodium or potassium.

Other suitable anionic surfactants are alkenyl or alkylbenzenesulfonates. The Alkenyl or alkyl group can be branched or linear and optionally with a Hydroxyl group may be substituted. The preferred alkylbenzenesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably from about 10 to 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. For mild surfactant systems, magnesium is preferred as the cation for Standard washing applications, however, sodium. The same applies to Alkenylbenzenesulfonates.

The term anionic surfactants also includes olefin sulfonates which are obtained by sulfonating C ₁₂ -C ₂₄ -, preferably C ₁₄ -C ₁₆ -α-olefins with sulfur trioxide and subsequent neutralization. Due to the manufacturing process, these olefin sulfonates can contain smaller amounts of hydroxyalkanesulfonates and alkane disulfonates. Special mixtures of α-olefin sulfonates are described in US 3,332,880.

Other preferred anionic surfactants are carboxylates, e.g. B. fatty acid soaps and comparable surfactants. The soaps can be saturated or unsaturated and can have various substituents, such as hydroxyl groups or α-sulfonate groups contain. Linear saturated or unsaturated are preferred Hydrocarbon residues as a hydrophobic portion with about 6 to about 30, preferably about 10 up to approx. 18 carbon atoms.

Other suitable anionic surfactants are salts of acylaminocarboxylic acids, the acyl sarcosinates formed in the alkaline medium by reaction of fatty acid chlorides with sodium sarcosinate; Fatty acid-protein condensation products obtained by reacting fatty acid chlorides with oligopeptides; Salts of alkyl sulfamidocarboxylic acids; Salts of alkyl and alkylaryl ether carboxylic acids; C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonation of the pyrolysis products of alkaline earth metal citrates, as described, for example, in GB-1,082,179; Alkylglycerol sulfates, oleylglycerol sulfates, alkylphenol ether sulfates, primary paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N-acyl taurides, alkyl succinates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ diester sulfates (especially saturated and unsaturated C ₁₂ -C ₁₈ diesters) unsaturated C ₁₂ -C ₁₈ diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxy carboxylates such as those of the formula RO (CH ₂ CH ₂ ) _k CH ₂ COO ^- M ⁺ , where RC ₈ to C ₂₂ -Alkyl, k is a number from 0 to 10 and M is a cation, resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acid. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch).

Polyethylen-, Polypropylen- und Polybutylenoxidkondensate von Alkylphenolen.

The following compounds, for example, are suitable as nonionic surfactants:

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.

These compounds include the condensation products of alkylphenols with a C ₆ to C ₂₀ alkyl group, which can be either linear or branched, with alkene oxides. Compounds with about 5 to 25 mol of alkene oxide per mol of alkylphenol are preferred. Commercially available surfactants of this type include Igepal® CO-630, Triton® X-45, X-114, X-100 and X102, and the ®Arkopal-N brands from Clariant GmbH. These surfactants are referred to as alkylphenol alkoxylates, for example alkylphenol ethoxylates.

Condensation products of aliphatic alcohols with approx. 1 to approx. 25 mol Ethylene oxide.

The alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. The condensation products of C ₁₀ to C ₂₀ alcohols with about 2 to about 18 moles of ethylene oxide per mole of alcohol are particularly preferred. The alkyl chain can be saturated or unsaturated. The alcohol ethoxylates can have a narrow ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates"). Examples of commercially available nonionic surfactants of this type are Teritol® 15-S-9 (condensation product of a linear secondary C ₁₁ -C ₁₅ alcohol with 9 mol ethylene oxide), Tergitol® 24-L-NMW (condensation product of a linear primary C ₁₂ -C ₁₄ -alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution). The Genapol® brands from Clariant GmbH also fall under this product class.

Condensation products of ethylene oxide with a hydrophobic base by condensation of propylene oxide with propylene glycol.

The hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800. The attachment of ethylene oxide to this Hydrophobic part leads to an improvement in water solubility. The product is liquid up to a polyoxyethylene content of approx. 50% of the total weight of the condensation product, which is a condensation with up to about 40 mol Corresponds to ethylene oxide. Commercially available examples of this product class are the Pluronic® brands from BASF and the ®Genapol PF brands from Clariant GmbH.

Condensation products of ethylene oxide with a reaction product of Propylene oxide and ethylenediamine.

The hydrophobic unit of these compounds consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a Molecular weight from about 2500 to 3000. At this hydrophobic unit Ethylene oxide up to a content of approx. 40 to approx. 80% by weight of polyoxyethylene and a molecular weight of about 5000 to 11000 added. Commercially available Examples of this class of compounds are the ®Tetronic brands from BASF and the ®Genapol PN brands from Clariant GmbH.

Semipolar nonionic surfactants

R ist hierbei eine Alkyl-, Hydroxyalkyl- oder Alkylphenolgruppe mit einer Kettenlänge von ca. 8 bis ca. 22 Kohlenstoffatomen, R² ist eine Alkylen- oder Hydroxyalkylengruppe mit ca. 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon, jeder Rest R¹ ist eine Alkyl- oder Hydroxyalkylgruppe mit ca. 1 bis ca. 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit ca. 1 bis ca. 3 Ethylenoxideinheiten und x bedeutet eine Zahl von 0 bis etwa 10. Die R¹-Gruppen können miteinander über ein Sauerstoff- oder Stickstoffatom verbunden sein und somit einen Ring bilden. Aminoxide dieser Art sind besonders C₁₀-C₁₈-Alkyldimethylaminoxide und C₈-C₁₂-Alkoxiethyl-Dihydroxyethylaminoxide.This category of nonionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each having an alkyl radical of from about 10 to about 18 carbon atoms. Semipolar nonionic surfactants are also amine oxides of the formula

R is an alkyl, hydroxyalkyl or alkylphenol group with a chain length of about 8 to about 22 carbon atoms, R ² is an alkylene or hydroxyalkylene group with about 2 to 3 carbon atoms or mixtures thereof, each R ¹ is an alkyl - Or hydroxyalkyl group with approx. 1 to approx. 3 carbon atoms or a polyethylene oxide group with approx. 1 to approx. 3 ethylene oxide units and x means a number from 0 to approx. 10. The R ¹ groups can be connected to one another via an oxygen or nitrogen atom and thus form a ring. Amine oxides of this type are especially C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxy diethyl dihydroxyethyl amine oxides.

fatty acid amides

Fatty acid amides have the formula RCO - N (R ¹ ) ₂ wherein R is an alkyl group with about 7 to about 21, preferably about 9 to about 17 carbon atoms and each radical R ^{1 is} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and (C ₂ H ₄ O) _x means H, where x varies from about 1 to about 3. C ₈ -C ₂₀ amides, monoethanolamides, diethanolamides and isopropanolamides are preferred.

Other suitable nonionic surfactants are alkyl and alkenyl oligoglycosides as well as fatty acid polyglycol esters or fatty amine polyglycol esters each with 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, alkoxylated triglycamides, Mixed ethers or mixed formals, alkyl oligoglycosides, alkenyl oligoglycosides, Fatty acid N-alkylglucamides, phosphine oxides, dialkyl sulfoxides and Protein.

worin R¹ C₈-C₂₂-Alkyl- oder -Alkenyl, R² Wasserstoff oder CH₂CO₂M, R³ CH₂CH₂OH oder CH₂CH₂OCH₂CH₂CO₂M, R⁴ Wasserstoff, CH₂CH₂OH oder CH₂CH₂COOM, Z CO₂M oder CH₂CO₂M, n 2 oder 3, bevorzugt 2, M Wasserstoff oder ein Kation wie Alkalimetall, Erdalkalimetall, Ammoniak oder Alkanolammonium bedeutet.Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkylamide betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium compounds of the formula

wherein R ^{1 is} C ₈ -C ₂₂ alkyl or alkenyl, R ^{2 is} hydrogen or CH ₂ CO ₂ M, R ³ CH ₂ CH ₂ OH or CH ₂ CH ₂ OCH ₂ CH ₂ CO ₂ M, R ^{4 is} hydrogen, CH ₂ CH ₂ OH or CH ₂ CH ₂ COOM, Z CO ₂ M or CH ₂ CO ₂ M, n 2 or 3, preferably 2, M is hydrogen or a cation such as alkali metal, alkaline earth metal, ammonia or alkanolammonium.

Preferred amphoteric surfactants of this formula are monocarboxylates and Dicarboxylates. Examples include cocoamphocarboxypropionate, Cocoamidocarboxypropionic acid, Cocoamphocarboxyglycinat (or also as Cocoamphodiacetate) and Cocoamphoacetat.

Further preferred amphoteric surfactants are alkyldimethylbetaines and Alkyldipolyethoxybetaines with an alkyl radical having about 8 to about 22 carbon atoms, which can be linear or branched, preferably having 8 to 18 carbon atoms and particularly preferably having about 12 to about 18 carbon atoms. These connections e.g. from Clariant GmbH under the trade name ®Genagen LAB marketed.

In special cases, the detergents and cleaning agents can also contain cationic surfactants. Suitable cationic surfactants are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R ¹ N (CH ₃ ) ₃ ^⊕ X ^⊖ , R ¹ R ² N (CH ₃ ) ₂ ^⊕ X ^⊖ , R ¹ R ² R ³ N (CH ₃ ) ^⊕ X ^⊖ or R ¹ R ² R ³ R ⁴ N ^⊕ X ^⊖ . The radicals R ^1, R ^2, R ³ and R ⁴ can preferably independently of one another unsubstituted alkyl with a chain length between 8 and 24 carbon atoms, in particular between 10 and 18 carbon atoms, hydroxyalkyl with about 1 to about 4 carbon atoms. Atoms, phenyl, C ₂ to C ₁₈ alkenyl, C ₇ to C ₂₄ aralkyl, (C ₂ H ₄ O) _x H, where x is from about 1 to about 3, one or more alkyl groups containing ester groups or cyclic quaternary ammonium salts. X is a suitable anion.

Other detergent and cleaning agent ingredients included in the present Invention may include include inorganic and / or organic Builders to reduce the hardness of the water.

These builders can range in weight from about 5% to about 80% Detergent and cleaning agent compositions may be included. inorganic Builders include, for example, alkali, ammonium and Alkanolammonium salts of polyphosphates such as tripolyphosphates, Pyrophosphates and glassy polymeric metaphosphates, phosphonates, silicates, Carbonates including bicarbonates and sesquicarbonates, sulfates and Aluminosilicates.

Examples of silicate builders are the alkali metal silicates, in particular those with an SiO ₂ : Na ₂ O ratio between 1.6: 1 to 3.2: 1, and layered silicates, for example sodium layered silicates, as described in US Pat. No. 4,664,839, available from Clariant GmbH under the SKS® brand. SKS-6® is a particularly preferred layered silicate builder.

Aluminosilicate builders are particularly preferred for the present invention. These are in particular zeolites with the formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] • xH ₂ O, where z and y are integers of at least 6, the ratio of z to y is between 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Suitable ion exchangers based on aluminosilicate are commercially available. This Aluminosilicates can be crystalline or amorphous in structure and can naturally occurring or synthetically produced. Procedure for the Production of ion exchangers based on aluminosilicate are described in US Pat. No. 3,985,669 and U.S. 4,605,509. Preferred ion exchangers based on synthetic Crystalline aluminosilicates are available under the name Zeolite A, Zeolite P (B) (including those disclosed in EP-A-0 384 070) and Zeolite X. Preferred are aluminosilicates with a particle diameter between 0.1 and 10 µm.

Suitable organic builders include polycarboxyl compounds such as for example ether polycarboxylates and oxydisuccinates, such as in U.S. 3,128,287 and U.S. 3,635,830. Also on "TMS / TDS" builders from U.S. 4,663,071.

Other suitable builders include the ether hydroxypolycarboxylates, Copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxy succinic acid, the alkali, ammonium and substituted ammonium salts of polyacetic acids such as e.g. Ethylenediaminetetraacetic acid and nitrilotriacetic acid, and Polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, Polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxy succinic acid, as well as their soluble salts.

Citrate-based builders, e.g. Citric acid and its soluble salts, especially the sodium salt, are preferred polycarboxylic acid builders that also in granulated formulations, especially together with zeolites and / or layered silicates can be used.

Other suitable builders are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in US 4,566,984.

If phosphorus-based builders can be used, and especially when soap bars for laundry are formulated by hand various alkali metal phosphates such as Sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate are used become. Phosphonate builders, such as ethane-1-hydroxy-1,1-diphosphonate, can also be used and other known phosphonates as described for example in U.S. 3,159,581, U.S. 3,213,030, U.S. 3,422,021, U.S. 3,400,148 and U.S. 3,422,137 are used.

In a preferred embodiment of the invention, the conventional ones Detergent ingredients from components typical of detergents, such as surfactants and builders can be selected. Possibly the detergent ingredients can include one or more cleaning aids or contain other materials that enhance the cleaning effect, for Treat or care for the object to be cleaned or the Change the usage properties of the detergent composition. Suitable cleaning aids include in detergent compositions the substances mentioned in US-3,936,537. The cleaning aids used in the Detergent compositions of the present invention can be used can include, for example, enzymes, especially proteases, lipases and Celluloses, foam boosters, foam brakes, start-up and / or Corrosion protection agents, suspending agents, dyes, fillers, optical brighteners, Disinfectants, alkalis, hydrotropic compounds, antioxidants, Enzyme stabilizers, perfumes, solvents, solubilizers, Redeposition inhibitors, dispersants, color transfer inhibitors, e.g. B. Polyamine N-oxides such as poly- (4-vinylpyridine-N-oxide), polyvinylpyrrolidone, poly-N-vinyl-N-methylacetamide and copolymers of N-vinylimidazole and N-vinylpyrrolidone, Processing aids, plasticizers and anti-static aids.

The detergent and detergent compositions of the present invention can optionally contain one or more conventional bleaches, as well as activators or stabilizers, in particular peroxy acids, which are not compatible with the Dirt-dissolving oligoesters according to the invention react. In general, must be sure that the bleach used with the Detergent ingredients are compatible. Conventional test methods, such as such as determining the bleaching activity of the formulated cleaning agent in Depending on the storage time can be used for this purpose.

The peroxy acid can either be a free peroxy acid or a combination from an inorganic persalt, for example sodium perborate or Sodium percarbonate and an organic peroxyacid precursor that leads to a Peroxyacid is converted when the combination of persalt and Peroxyacid precursor is dissolved in water. The organic peroxyacid precursors are often referred to as bleach activators in the prior art.

Examples of suitable organic peroxyacids are disclosed in US 4,374,035, U.S. 4,681,592, U.S. 4,634,551, U.S. 4,686,063, U.S. 4,606,838 and U.S. 4,671,891. Examples of compositions suitable for bleaching laundry and containing perborate bleaches and activators are described in U.S. 4,412,934, U.S. 4,536,314, U.S. 4,681,695 and U.S. 4,539,130.

Examples of peroxyacids preferred for use in this invention are peroxydodecanedioic acid (DPDA), the nonylamide of Peroxysuccinic acid (NAPSA), the nonyl amide of peroxyadipic acid (NAPAA) and decyldiperoxy succinic acid (DDPSA). The peroxy acid is preferably in contain a soluble granulate, according to the method from US-4,374,035. A preferred bleaching granulate contains, in percent by weight, 1% to 50% of one exothermic soluble compound such as boric acid; 1% to 25% of one with the peroxyacid-compatible surfactant, such as for example C13LAS; 0.1% to 10% of one or more chelate stabilizers, such as sodium pyrophosphate; and 10% to 70% of a water soluble Salt such as sodium sulfate.

The peroxyacid bleaching agent is used in amounts equal to an amount of available oxygen between about 0.1% to about 10%, preferably between about 0.5% to about 5%, in particular from about 1% to 4%. The percentages relate to the total weight of the Detergent composition.

Suitable amounts of the peroxyacid-containing bleaching agent, based on a Unit dose of the detergent composition according to the invention as it is is used for a typical wash liquor containing about 65 liters of water from 15 to 60 ° C, produce between about 1 ppm to about 150 ppm available Oxygen, preferably between about 2 ppm to about 20 ppm Oxygen. The wash liquor should have a pH between 7 and 11, preferably between 7.5 and 10.5 in order to obtain a sufficient bleaching result achieve. Reference is made to column 6, lines 1 to 10 of US 4,374,035.

Alternatively, the bleach composition can be an appropriate one organic peroxyacid precursor containing one of the above Peroxyacids generated when in an aqueous alkaline solution Hydrogen peroxide reacts. The source of the hydrogen peroxide can be any inorganic peroxide, which releases hydrogen peroxide in aqueous solution, such as sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.

The proportion of the peroxide-containing bleaching agents in the inventive Detergent compositions range from about 0.1% to about 95% by weight % By weight, and preferably between about 1% by weight and about 60% by weight. If the bleach composition is also fully formulated Detergent composition, it is preferred that the proportion of the peroxide-containing bleaching agent is between about 1% by weight to about 20% by weight.

The amount of bleach activators with the invention Soil release oligoesters can generally be used between 0.1 and 60% by weight, preferably between 0.5 and 40% by weight. Are the used Bleach compositions fully formulated at the same time Detergent compositions, the amount of bleach activators, which is in is contained, preferably between about 0.5 and 20 wt .-%.

The peroxyacid and the soil release oligoester according to the invention are preferred in a weight ratio between available oxygen from the peroxyacid to the soil release oligoester according to the invention from about 4: 1 to about 1:30, especially from about 2: 1 to about 1:15, and especially from about 1: 1 to about 1: 7.5 in front. This combination can be used both as a fully formulated product and as Additive to a detergent can be used.

The washing and cleaning agents according to the invention can have one or more contain conventional enzymes that are not compatible with the invention Soil release oligoesters of this invention react. A particularly preferred one The enzyme is cellulose. The cellulose used here can be made from bacteria or Mushrooms are obtained and should have an optimal pH range between 5 and 9.5 exhibit. Suitable celluloses are disclosed in US 4,435,307. It is about cellulose produced by a strain of Humicola insolens, especially from the Humicola DSM 1800 strain or another cellulose-212 producing Mushroom, which belongs to the genus Aeromonas, and cellulose, which from certain marine molluscs have been extracted from the hepatopancreas. suitable Celluloses are also in GB-A-2,075,028, GB-A-2,085,275 and DE-OS-2,247,832.

Preferred celluloses are described in WO-91/17243. The invention Detergent compositions contain enzymes in amounts up to about 50 mg, preferably from about 0.01 mg to about 10 mg per gram of Detergent composition. Based on the weight of the washing and Detergent compositions comprising the invention Containing soil release oligoester, the proportion of enzymes is at least 0.001% by weight, preferably between about 0.001% by weight to about 5% by weight, in particular from about 0.001% by weight to about 1% by weight, especially from about 0.01% to about 1% by weight.

Examples: example 1

1000 g of a sec. Alkanesulfonate (commercial product ®Hostapur SAS 93 pellets) were mixed intensively with 10 g calcium stearate and then ground on a beater wheel mill without internals with a product throughput of 55 kg / h. An easily pourable granulate with the following grain size distribution was obtained: 0.1-0.6 mm 18% 0.6 - 1.0 mm 34% 1.0 - 2.0 mm 33% > 2.0 mm 15%

Example 2

1000 g sec. Alkane sulfonate as in Example 1 was mixed intensively with 10 g of silica (Sipernat® 22 S) and then ground on a beater wheel mill without internals with a product throughput of 60 kg / h. An easily pourable granulate with the following particle size distribution was obtained: 0.1-0.6 mm 25% 0.6-1.0 mm 46% 1.0 - 2.0 mm 19% > 2.0 mm 10%

Example 3

1000 g sec. Alkanesulfonate as in Example 1 was mixed intensively with 10 g of calcium stearate and then ground on a laboratory screen basket mill (universal mill with cross beater) with a product throughput of 70 kg / h. The hole diameter of the strainer was 6 mm.
An easily pourable granulate with a bulk density of 519 g / l and the following grain size distribution was obtained: 0.1-0.6 mm 43% 0.6 - 1.0 mm 48% 1.0 - 2.0 mm 9%

Example 4

Example 3 was repeated, Mg stearate being used as the additive instead of Ca stearate. The free-flowing granules obtained had a bulk density of 519 g / l and the following particle size distribution: 0.1-0.6 mm 26% 0.6 - 1.0 mm 64%% 1.0 - 2.0 mm 10%

Example 5

1000 g sec. Alkanesulfonate as in Example 1 were mixed with 20 g of a premix of magnesium oxide and magnesium silicate = 1: 1. The pellets treated in this way were ground on a laboratory sieve basket mill with a hole size of 8 mm and a product throughput of 40 kg / h. A free-flowing granulate with the following grain size distribution was obtained: 0.1-1.0 mm 39% 1.0 - 2.0 mm 58% > 12 mm 3%

Example 6

5000 g sec. Alkanesulfonate as in Example 1 was premixed with 50 g of hydrophobic silica (Sipernat D 17) and ground on a laboratory screen grinder with a hole size of 6 mm and a product throughput of 60 kg / h. The granules obtained had the following grain size distribution: 0.1-1.0 mm 81% 1.0 - 2.0 mm 19%

Example 7

5000 g sec. Alkanesulfonate as in Example 1 were treated with 100 g of hydrophilic silica (Sipernat® 22 S) and ground as described in Example 3. The bulk density of the free-flowing granules was 532 g / l. A sieve analysis showed the following grain size distribution: 0.1-1.0 mm 88% 1.0 - 2.0 mm 12%

Example 8

Secondary alkanesulfonate was mixed with 1% by weight of silica (Sipernat D 17) and ground on a Pallmann mill (Pallmann PP6 mill with sieve basket and turbine). The strainer basket consists of a perforated plate with 6 mm rectangular perforation. The product throughput was 500 kg / h. The bulk density of the free-flowing granules was 590 g / l. A sieve analysis showed the following grain size distribution: 0.1-1.0 mm 95% 1.0 - 2.0 mm 5%

Claims (2)

1. A process for preparing a pulverulent or granular secondary alkanesulfonate essentially comprising finely divided, solid secondary alkanesulfonate and a nonhygroscopic additive, which comprises grinding the secondary alkanesulfonate together with the additive to a particle size of from 0.1 to 3 mm, the amount of additive being from 0.1 to 10 %, based on the secondary alkanesulfonate.
2. A process as claimed in claim 1, which comprises grinding the secondary alkanesulfonate together with silica as additive.