EP0966510B1 - Preparation de sulfonate d'alcane secondaire granulaire - Google Patents

Preparation de sulfonate d'alcane secondaire granulaire Download PDF

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Publication number
EP0966510B1
EP0966510B1 EP98906864A EP98906864A EP0966510B1 EP 0966510 B1 EP0966510 B1 EP 0966510B1 EP 98906864 A EP98906864 A EP 98906864A EP 98906864 A EP98906864 A EP 98906864A EP 0966510 B1 EP0966510 B1 EP 0966510B1
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EP
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Prior art keywords
alkyl
alkanesulfonate
acid
preferred
weight
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EP98906864A
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German (de)
English (en)
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EP0966510A1 (fr
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Frank-Peter Lang
Helmut Kramer
Roland Steinl
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • SAS Secondary alkane sulfonates
  • 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.
  • 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.
  • Alkanesulfonate for example in the form of Pellets (Hostapur® SAS 93) or in the form of flakes.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 (®A
  • 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.
  • 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.
  • 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.
  • 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
  • M is a hydrogen atom or a cation such as, for , As sodium, potassium, lithium, calcium, magnesium, ammonium or a substituted ammonium cation.
  • 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.
  • 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.
  • alkenyl or alkylbenzenesulfonates 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.
  • magnesium is preferred as the cation for Standard washing applications, however, sodium.
  • Alkenylbenzenesulfonates are alkenyl or alkylbenzenesulfonates.
  • 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 ⁇ -olefin sulfonates are described in US 3,332,880.
  • Suitable 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 ⁇ -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.
  • 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
  • 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.
  • 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").
  • 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).
  • Genapol® brands from Clariant GmbH also fall under this product class.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • R 1 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • X is a suitable anion.
  • 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.
  • 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.
  • 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 ⁇ m.
  • 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.
  • 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.
  • polyacetic acids such as e.g. Ethylenediaminetetraacetic acid and nitrilotriacetic acid
  • Polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic
  • 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.
  • 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.
  • the conventional ones Detergent ingredients from components typical of detergents, such as surfactants and builders can be selected.
  • 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 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.
  • enzymes especially proteases, lipases and Celluloses
  • foam boosters 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.
  • 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.
  • 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.
  • 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).
  • DPDA peroxydodecanedioic acid
  • NAPSA nonylamide of Peroxysuccinic acid
  • NAPAA nonyl amide of peroxyadipic acid
  • DDPSA decyldiperoxy succinic acid
  • 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.
  • one exothermic soluble compound such as boric acid
  • 1% to 25% of one with the peroxyacid-compatible surfactant such as for example C13LAS
  • one or more chelate stabilizers such as sodium pyrophosphate
  • 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.
  • 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.
  • Soil release oligoesters can generally be used between 0.1 and 60% by weight, preferably between 0.5 and 40% by weight.
  • 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.
  • 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.
  • 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%
  • 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 2 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%

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (2)

  1. Procédé pour la préparation d'un alcanesulfonate secondaire sous forme de poudre ou de granulat, constitué essentiellement d'un alcanesulfonate solide secondaire, finement divisé et d'un additif non hygroscopique, caractérisé en ce qu'on broie l'alcanesulfonate secondaire avec l'additif à une taille de grains de 0,1 à 3 mm, la quantité d'additif s'élevant de 0,1 à 10 %, par rapport à l'alcanesulfonate secondaire.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on broie l'alcane sulfonate secondaire avec de l'acide silicique comme additif.
EP98906864A 1997-01-21 1998-01-09 Preparation de sulfonate d'alcane secondaire granulaire Expired - Lifetime EP0966510B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19701896A DE19701896A1 (de) 1997-01-21 1997-01-21 Granulares sekundäres Alkansulfonat
DE19701896 1997-01-21
PCT/EP1998/000089 WO1998031775A1 (fr) 1997-01-21 1998-01-09 Sulfonate d'alcane secondaire granulaire

Publications (2)

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EP0966510A1 EP0966510A1 (fr) 1999-12-29
EP0966510B1 true EP0966510B1 (fr) 2003-10-22

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US (1) US6051544A (fr)
EP (1) EP0966510B1 (fr)
JP (2) JP4263246B2 (fr)
AR (1) AR011543A1 (fr)
AU (1) AU6292198A (fr)
DE (2) DE19701896A1 (fr)
ES (1) ES2210725T3 (fr)
WO (1) WO1998031775A1 (fr)

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DE19944218A1 (de) * 1999-09-15 2001-03-29 Cognis Deutschland Gmbh Waschmitteltabletten
DE19956803A1 (de) * 1999-11-25 2001-06-13 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE19956802A1 (de) * 1999-11-25 2001-06-13 Cognis Deutschland Gmbh Waschmitteltabletten
EP1201741A1 (fr) * 2000-10-31 2002-05-02 The Procter & Gamble Company Compositions détergentes
DE102004017112B4 (de) * 2004-04-07 2007-06-28 Henkel Kgaa Verwendung von Pudermittel
DE102007028310A1 (de) * 2007-06-20 2008-12-24 Clariant International Ltd. Tensidmischungen mit synergistischen Eigenschaften
DE102007034540A1 (de) * 2007-07-20 2009-01-22 Henkel Ag & Co. Kgaa Bügel-Pad mit fester Fleckbehandlungszusammensetzung
DE102008013606A1 (de) 2008-03-11 2009-09-17 Clariant International Ltd. Verfahren zur Herstellung fester Erdalkalimetallsalze sekundärer Paraffinsulfonsäuren
BRPI1014899B1 (pt) * 2009-04-24 2019-11-05 Unilever Nv processo para produção de partículas detergente
DE102010055742A1 (de) 2010-12-22 2012-06-28 Clariant International Ltd. Zusammensetzungen enthaltend sekundäres Paraffinsulfonat und Alkoholalkoxylat
DE102010055743A1 (de) * 2010-12-22 2012-06-28 Clariant International Ltd. Zusammensetzungen enthaltend sekundäres Paraffinsulfonat und Alkoholalkoxylat
DE102010055741A1 (de) * 2010-12-22 2012-06-28 Clariant International Ltd. Zusammensetzungen enthaltend sekundäres Paraffinsulfonat und Tetrahydroxypropylethylendiamin
CN105324477B (zh) * 2013-06-13 2018-04-06 宝洁公司 颗粒状衣物洗涤剂
US9828569B2 (en) 2013-06-13 2017-11-28 The Procter & Gamble Company Granular laundry detergent
DE102014009836B4 (de) 2014-07-03 2017-04-06 Weylchem Wiesbaden Gmbh Natriumsalze sekundärer Alkansulfonate enthaltende Compounds, ihre Herstellung und Verwendung sowie Wasch-, Desinfektion- und Reinigungsmittel enthaltend diese
EP3484772B1 (fr) 2016-07-18 2023-12-20 Azurity Pharmaceuticals, Inc. Appareil et procédé pour remplir un récipient de matériaux en vrac
CN114949928A (zh) * 2022-06-08 2022-08-30 史宏霞 一种低熔点表面活性剂粉剂化的制备方法及其应用

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Publication number Publication date
ES2210725T3 (es) 2004-07-01
JP2001508118A (ja) 2001-06-19
JP5124379B2 (ja) 2013-01-23
AU6292198A (en) 1998-08-07
EP0966510A1 (fr) 1999-12-29
DE59809971D1 (de) 2003-11-27
JP4263246B2 (ja) 2009-05-13
US6051544A (en) 2000-04-18
DE19701896A1 (de) 1998-07-23
JP2008285683A (ja) 2008-11-27
WO1998031775A1 (fr) 1998-07-23
AR011543A1 (es) 2000-08-30

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