EP0966510A1

EP0966510A1 - Granular secondary alkane sulphonate

Info

Publication number: EP0966510A1
Application number: EP98906864A
Authority: EP
Inventors: Frank-Peter Lang; Helmut Kramer; Roland Steinl
Original assignee: Clariant GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 1997-01-21
Filing date: 1998-01-09
Publication date: 1999-12-29
Anticipated expiration: 2018-01-09
Also published as: JP2008285683A; ES2210725T3; WO1998031775A1; US6051544A; DE19701896A1; EP0966510B1; AR011543A1; AU6292198A; JP5124379B2; JP4263246B2; JP2001508118A; DE59809971D1

Abstract

The invention concerns a granular secondary alkane sulphonate essentially comprising fine-particle solid secondary alkane sulphonate and an additive. This granular secondary alkane sulphonate is obtained by grinding and mixing coarse secondary alkane sulphonate with an additive, preferably fine-particle silicic acid. The alkane sulphonate prepared in this way can be used in solid washing and cleaning agents or directly for producing extrudates, mouldings or compacts.

Description

Granular secondary alkanesulfonate

Secondary alkanesulfonates (SAS) have been an important product group within the anionic surfactants for many years. However, secondary alkanesulfonate in solid form has the undesirable property that it is hygroscopic. Due to this property, solid SAS is only marketed as pellets or flakes. The hygroscopic property of the SAS does not play a role in this rough form. For the production of powdery, homogeneous washing and cleaning agents, however, it is necessary that all components are in finely divided form. Fine-particle SAS agglomerates due to its hygroscopic property, so that powdered detergents and cleaning agents containing SAS do not remain in the fine-particle 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 detergents and cleaning agents.

DE-A-2 415 159 describes a product which is obtained by spray drying an aqueous solution of alkanesulfonate and a carrier material. Inorganic salts are essentially suitable as carrier material. 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 spray neutralization, in which the anionic surfactants are sprayed in their acid form together with aqueous solutions of bases. Suitable dust-binding additives can be 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 containing no additive or anti-caking agent. The present invention has for its object to provide solid SAS in finely divided form, which can be incorporated directly as a surfactant component in powder detergents and cleaning agents without the formation of agglomerates or in the usual way together with components customary in detergents and cleaning agents can be processed further to solid extrudates, compacts or compactates.

The invention relates to a granular secondary alkanesulfonate consisting essentially of finely divided solid sec. Alkanesulfonate and an 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 alkane sulfonate, the alkyl group can be either saturated or unsaturated, branched 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 having no sulfonate groups. The preferred secondary alkanesulfonates contain linear alkyl chains with about 9-25 carbon atoms, preferably 10 to 20, and particularly preferably about 13 to 17 carbon atoms. The cation is, for example, sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Sodium as the cation is preferred.

The alkanesulfonate according to the invention is prepared by grinding SAS in the form of pellets or flakes, as are usually obtained in the production of solid SAS. In a first embodiment, this coarse SAS is mixed intensively with the additive before grinding and then ground. In principle, all grinding devices, such as. B. impact mills, granulators, roller mills or air jet mills. Impact mills are, for example, impact wheel mills with and without internals, pin mills and disintegrators, especially with ground pins, universal mills with various working elements, especially with hammer-like working elements. Cutting mills, universal mills with cross beater and baffle plate mills with screen basket and beater cross / turbine (for example baffle plate mills from Type PP / PPS from Pallmann).

As an alternative to this, it is also possible to dispense with a premixing of alkanesulfonate and additive and to add the additive simultaneously with the alkanesulfonate directly into the grinding device. Coarser materials with a diameter in the millimeter range can then also be used, since these are themselves comminuted during grinding and intensively mixed with the alkanesulfonate due to the mechanical action.

The mixture of alkanesulfonate and additive can be ground with cooling in order to dissipate the frictional heat and to support the comminution process by embrittlement at low temperatures. For this purpose, either the mill can be cooled directly or the air flow sucked in by the mill is cooled if it is a continuous grinding process. You can also see the sec. Pre-cool the alkanesulfonate or add a refrigerant such as dry ice during the grinding process. With this shredding process, care must be taken to ensure that the entry of moisture, in particular the atmospheric humidity after grinding (until the product temperature has adjusted to the ambient temperature), e.g. is avoided by equipment measures.

According to a third variant, it is also possible first to grind the coarse solid SAS, preferably with cooling, as described above, and then to mix the ground SAS with the additive.

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

A large number of compounds are suitable as additives in the context of this invention. They can be water-soluble, but they are preferably hydrophobic. In any case, the prerequisite is that these additives are not hygroscopic. Also preferred are those additives that are already present in 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, silicic acid, talc, talc. Alkaline earth sulfates. 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, Sipernat 50, Sipernat 50 S, Sipernat D 17, © Ultrasil VN 2, Ultrasil VN 3, © Wessalon and Wessalon S from Degussa. Such silicas are inherently 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. Alkanesulfonate can be used immediately can be incorporated as a surfactant component in detergents and cleaning agents. 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 powdered 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. Alkane sulfonate can be used in the finished detergent and cleaning agent formulations either alone or in combination with other surfactants.

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

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

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. 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

R ¹ CH COOR

I SO ₃ M

where R ^{1 is} a C ₈ -C ₂₀ hydrocarbon radical, preferably alkyl, and R is a C _r 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 JVIonoethanolamin, 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 S0 ₃ M, in which R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl radical represents 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 substituted with a hydroxyl group. The preferred alkylbenzenesulfonates contain linear alkyl chains with about 9 to 25 carbon atoms, preferably from about 10 to about 13 carbon atoms, the cation is sodium, potassium, ammonium, mono-, di- or triethanolammonium, calcium or magnesium and mixtures thereof. Magnesium is preferred as the cation for mild surfactant systems, while sodium is preferred for standard washing applications. 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 - 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 hydrocarbon radicals are preferred as the hydrophobic portion with approximately 6 to approximately 30, preferably approximately 10 to approximately 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 alkylsulfamidocarboxylic 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 ₂ -C ₁₈ diester sulfates (especially saturated and unsaturated C ₂ -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 acids.Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz , Perry and Berch).

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

Question:

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols.

These compounds include the condensation products of alkyl phenols 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 are, for example, 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 (the condensation product of a linear secondary C _{ι r} C ₁₅ alcohol with 9 moles ethylene oxide), Tergitol ^® 24-L-NMW (the 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, formed by the condensation of propylene oxide with propylene glycol.

The hydrophobic part of these compounds preferably has a molecular weight between approximately 1500 and approximately 1800. The addition 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 corresponds to a condensation with up to approx. 40 mol 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 of approximately 2500 to 3000. Ethylene oxide is added to this hydrophobic unit up to a content of approximately 40 to approximately 80% by weight of polyoxyethylene and a molecular weight of approximately 5000 to 11000. 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

This category of non-ionic compounds includes water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides, each with an alkyl radical of about 10 to about 18 carbon atoms. Semipolar nonionic surfactants are also amine oxides of the formula

O

R (OR ² ) _χ N (R ¹ ) ₂

R here 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 radical 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 in particular C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyl-dihydroxyethylamine 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 _r C ₄ -alkyl, C _r C ₄ -hydroxyalkyl and (C ₂ H ₄ 0 ) _x means H, where x varies from approx. 1 to approx. 3. C ₈ -C ₂₀ amides, monoethanolamides, diethanolamides and isopropanolamides are preferred.

Further suitable nonionic surfactants are alkyl and alkenyl oligoglycosides as well as fatty acid polyglycol esters or fatty amine polyglycol esters each having 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-alkyuloxoxide and fatty acid-N-alkyuloxoxide-fatty acids-N-alkyuloxoxide-fatty acid-N-alkylyoxoxide-fatty acids-N-alkyuloxoxide-fatty acids-N-alkylyoxoxide-fatty acids-N-alkylyoxoxide-fatty acids Protein hydrolyzates.

Typical examples of amphoteric or zwitterionic surfactants are alkyl betaines, alkylamide betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium compounds of the formula

R ¹

wherein R ^{1 is} C ₈ -C ₂₂ alkyl or alkenyl, R ^{2 is} hydrogen or CH ₂ C0 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 means 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, cocoamphocarboxyglycinate (or also known as cocoamphodiacetate) and cocoamphoacetate.

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

In special cases, the washing 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 ^a X ^θ , R ¹ R ² N (CH ₃ ) ₂ ^Θ X ^Θ , R ¹ R ² R ³ N (CH ₃ ) ^Θ X ^Θ or R ¹ R ² R ³ RN ^Φ X ^Θ . 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 C atoms, in particular between 10 and 18 C atoms, hydroxyalkyl with approx. 1 to approx. 4 C - Atoms, phenyl, C ₂ to C ₁₈ alkenyl, C ₇ to C ₂₄ aralkyl, (C ₂ H ₄ 0) _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 that may be included in the present invention include inorganic and / or organic builders to reduce the hardness of the water.

These builders can be present in the detergent and cleaning agent compositions in a proportion by weight of about 5% to about 80%. 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 sheet silicates, for example sodium sheet silicates, as described in. US Pat. No. 4,664,839, available from Clariant GmbH under of 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 0, where z and y are integers of at least 6, the ratio of z to y 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. These aluminosilicates can be crystalline or amorphous in structure, and can be naturally occurring or synthetic. Methods for the production of ion exchangers based on aluminosilicate are described in US Pat. Nos. 3,985,669 and 4,605,509. Preferred ion exchangers based on synthetic crystalline aluminosilicates are available under the names 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 ether polycarboxylates and oxydisuccinates, as described, for example, in US Pat. Nos. 3,128,287 and 3,635,830. Reference should also be made to "TMSTDS" builders from US 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 also polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxy succinic acid, and their soluble salts.

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

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 if hand soap bars are to be formulated for washing, various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates such as those disclosed in, for example, US-3, 159,581, US-3,213,030, US-3,422,021, US-3,400,148 and US-3,422,137 can also be used .

In a preferred embodiment of the invention, the conventional detergent ingredients can be made from components typical of detergents, such as surfactants and builders can be selected. Optionally, the detergent ingredients can contain one or more cleaning aids or other materials that enhance the cleaning effect, serve to treat or care for the object to be cleaned or change the performance properties of the detergent composition. Suitable cleaning aids in detergent compositions include those mentioned in US 3,936,537. The cleaning aids that can be used in the detergent compositions of the present invention include, for example, enzymes, in particular proteases, lipases and celluloses, foam boosters, foam retardants, tarnishing and / or anti-corrosion agents, suspending agents, dyes, fillers, optical brighteners, disinfectants, alkalis, hydrotropes 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-vinyipyrrolidone, processing aids, plasticizers and antistatic aids.

The detergent and cleaning agent compositions of the present invention may optionally contain one or more conventional bleaches, and activators or stabilizers, in particular peroxyacids, which do not react with the soil release oligoesterπ according to the invention. In general, it must be ensured that the bleaching agents used are compatible with the detergent ingredients. Conventional test methods, such as determining the bleaching activity of the formulated cleaning agent depending on the storage time, can be used for this purpose.

The peroxyacid can be either a free peroxyacid or a combination of an inorganic persalt, e.g. sodium perborate or sodium percarbonate, and an organic peroxyacid precursor which is converted to a peroxyacid when the combination of the persalt and the peroxyacid precursor is dissolved in water. The organic peroxyacid precursors are often referred to in the art as bleach activators. Examples of suitable organic peroxyacids are disclosed in U.S. 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 include peroxydodecanedioic acid (DPDA), nonylamide of peroxysuccinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) and decyldiperoxysuccinic acid (DDPSA). The peroxyacid is preferably contained in a soluble granulate, according to the method from US-4,374,035. A preferred bleach granulate contains, in percent by weight, 1% to 50% of an exothermic soluble compound, such as, for example, boric acid; 1% to 25% of a surfactant compatible with the peroxyacid, such as 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 that provide an amount of available oxygen between about 0.1% to about 10%, preferably between about 0.5% to about 5%, especially about 1% to 4%. The percentages relate to the total weight of the detergent composition.

Suitable amounts of the peroxyacid bleach based on a unit dose of the detergent composition of the invention as used for a typical wash liquor comprising about 65 liters of water at 15 to 60 ° C produce between about 1 ppm to about 150 ppm available oxygen, preferably between about 2 ppm to about 20 ppm available oxygen. The wash liquor should have a pH between 7 and 11, preferably between 7.5 and 10.5, in order to achieve a sufficient bleaching result. Reference is made to column 6, lines 1 through 10 of US 4,374,035. Alternatively, the bleaching composition may contain a suitable organic peroxyacid precursor which produces one of the above-mentioned peroxyacids when it reacts with hydrogen peroxide in an aqueous alkaline solution. The source of hydrogen peroxide can be any inorganic peroxide that releases hydrogen peroxide in aqueous solution, such as sodium perborate (monohydrate and tetrahydrate) and sodium percarbonate.

The proportion of bleaching agents containing peroxide in the cleaning agent compositions according to the invention is between about 0.1% by weight to about 95% by weight and preferably between about 1% by weight and about 60% by weight. When the bleach composition is also a fully formulated detergent composition, it is preferred that the proportion of the peroxide-containing bleach be between about 1% to about 20% by weight.

The amount of bleach activators that can be used with the soil release oligoesters according to the invention is generally between 0.1 and 60% by weight, preferably between 0.5 and 40% by weight. If the bleaching agent compositions used are at the same time completely formulated detergent compositions, the amount of bleach activators contained in them is preferably between about 0.5 and 20% by weight.

The peroxy acid and the soil release oligoester according to the invention are preferably in a weight ratio between the available oxygen from the peroxy acid and the soil release oligoester according to the invention of from about 4: 1 to about 1:30, in particular from about 2: 1 to about 1:15, and especially from about 1: 1 to about 1: 7.5. This combination can be used both as a fully formulated product and as an additive to a detergent.

The washing and cleaning agents according to the invention can contain one or more conventional enzymes which do not react with the soil release oligoester according to the invention of this invention. A particularly preferred enzyme is cellulose. The cellulose used here can be obtained from bacteria or fungi and should have an optimal pH range between 5 and 9.5 exhibit. Suitable celluloses are disclosed in US 4,435,307. It is cellulose which is produced by a strain of Humicola insolens, in particular the strain Humicola DSM 1800 or another cellulose-212-producing fungus which belongs to the genus Aeromonas, and cellulose which extracts from the hepatopancreas of certain marine mollusks has been. Suitable celluloses are also disclosed 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 detergent compositions according to the invention contain enzymes in amounts of up to about 50 mg, preferably from about 0.01 mg to about 10 mg, per gram of the detergent composition. Based on the weight of the detergent and cleaning agent compositions which contain the soil release oligoesters according to the invention, the proportion of the enzymes is at least 0.001% by weight, preferably between about 0.001% by weight and about 5% by weight, in particular 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) was 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 particle 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. Alkanesulfonate as in Example 1 were mixed with 10 g of silica (Sipernat®

22 S) mixed intensively and then on one

Mill the beater wheel mill without internals with a product throughput of 60 kg / h. It became a free-flowing granulate with the following

Obtain grain size distribution:

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 particle 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 made with 20 g of a premix

Magnesium oxide and magnesium silicate = 1: 1 mixed. The pellets treated in this way were placed on a laboratory sieve basket mill with a hole size of 8 mm and a

Grind product throughput of 40 kg / h. A free-flowing granulate with the following particle size distribution was obtained:

0.1-1.0 mm 39%

1.0 -2.0 mm 58%

> 12mm 3%

Example 6

5000 g sec. Alkane sulfonate as in Example 1 became more hydrophobic with 50 g

Silicic acid (Sipernat D 17) premixed 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 became more hydrophilic with 100 g

Treated silica (Sipernat® 22 S) and grind 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 on a Pallmann mill (Pallmann PP6 mill with sieve basket and

Turbine) ground. The sieve basket consists of a perforated plate with a 6 mm

Rectangular perforation. The product throughput was 500 kg / h. The bulk density of the free-flowing granules was 590 g / l. Screen analysis revealed the following

Grain size distribution:

0.1 - 1.0 mm 95%

1.0 - 2.0 mm 5%

Claims

Claims:

1. Granular secondary alkanesulfonate, consisting essentially of finely divided, solid secondary alkanesulfonate and an additive.

2. Granular secondary alkanesulfonate according to claim 1, characterized in that the additive is a silica.

3. Granular secondary alkane sulfonate according to claim 1, containing 0.1 to 10 wt .-% of the additive, based on the amount of secondary alkane sulfonate.

4. Powdered washing and cleaning agents containing a granular secondary alkanesulfonate according to claim 1.

5. extrudates, compacts and compactates containing a granular secondary alkanesulfonate according to claim 1.