EP0966510A1 - Granulares sekundäres alkansulfonat - Google Patents
Granulares sekundäres alkansulfonatInfo
- Publication number
- EP0966510A1 EP0966510A1 EP98906864A EP98906864A EP0966510A1 EP 0966510 A1 EP0966510 A1 EP 0966510A1 EP 98906864 A EP98906864 A EP 98906864A EP 98906864 A EP98906864 A EP 98906864A EP 0966510 A1 EP0966510 A1 EP 0966510A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- alkanesulfonate
- acid
- additive
- alkane sulphonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
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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
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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
- 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
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
Definitions
- SAS Secondary alkanesulfonates
- 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.
- the invention relates to a granular secondary alkanesulfonate consisting essentially of finely divided solid sec. Alkanesulfonate and an additive.
- Alkanesulfonate for example in the form of pellets (Hostapur® SAS 93) or in the form of flakes.
- 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.
- this coarse SAS is mixed intensively with the additive before grinding and then ground.
- 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.
- 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.
- 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.
- 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.
- 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 sulfates 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%.
- 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 is a C 8 -C 20 hydrocarbon radical, preferably alkyl
- 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.
- 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 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 .
- 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 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.
- 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 hydrocarbon radicals are preferred as the hydrophobic portion with approximately 6 to approximately 30, preferably approximately 10 to approximately 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 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,
- 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.
- 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 (the condensation product of a linear secondary C ⁇ 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).
- Teritol® 15-S-9 the condensation product of a linear secondary C ⁇ 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.
- 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 consist 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.
- 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
- 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
- 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 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.
- 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-N-alkylyoxoxide-fatty acids Protein hydrolyzates.
- amphoteric or zwitterionic surfactants are alkyl betaines, alkylamide betaines, aminopropionates, aminoglycinates, or amphoteric imidazolinium compounds of the formula
- 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.
- 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.
- 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 ⁇ , 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 RN ⁇ 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 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.
- 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 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 ⁇ m.
- 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.
- 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.
- polyacetic acids such as e.g. Ethylenediaminetetraacetic acid and nitrilotriacetic acid
- polycarboxylic acids such as mellitic acid, succinic acid, oxydisuccinic acid, poly
- 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.
- 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 .
- the conventional detergent ingredients can be made from components typical of detergents, such as surfactants and builders can be selected.
- 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.
- 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 oligoester ⁇ according to the invention.
- activators or stabilizers in particular peroxyacids, which do not react with the soil release oligoester ⁇ according to the invention.
- peroxyacids which do not react with the soil release oligoester ⁇ according to the invention.
- 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.
- 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).
- DPDA peroxydodecanedioic acid
- NAPSA nonylamide of peroxysuccinic acid
- NAPAA nonylamide of peroxyadipic acid
- DDPSA decyldiperoxysuccinic acid
- 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.
- an exothermic soluble compound such as, for example, boric acid
- a surfactant compatible with the peroxyacid such as C13LAS
- chelate stabilizers such as sodium pyrophosphate
- 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.
- 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.
- 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.
- 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.
- 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 laboratory screen basket mill universal mill with cross beater
- Hole diameter of the strainer was 6 mm.
- 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:
- 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
- Treated silica (Sipernat® 22 S) and grind as described in Example 3.
- the bulk density of the free-flowing granules was 532 g / l.
- the sieve basket consists of a perforated plate with a 6 mm
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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)
Abstract
Description
Claims
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 (de) | 1997-01-21 | 1998-01-09 | Granulares sekundäres alkansulfonat |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0966510A1 true EP0966510A1 (de) | 1999-12-29 |
EP0966510B1 EP0966510B1 (de) | 2003-10-22 |
Family
ID=7817883
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98906864A Expired - Lifetime EP0966510B1 (de) | 1997-01-21 | 1998-01-09 | Herstellung von granularem sekundärem alkansulfonat |
Country Status (8)
Country | Link |
---|---|
US (1) | US6051544A (de) |
EP (1) | EP0966510B1 (de) |
JP (2) | JP4263246B2 (de) |
AR (1) | AR011543A1 (de) |
AU (1) | AU6292198A (de) |
DE (2) | DE19701896A1 (de) |
ES (1) | ES2210725T3 (de) |
WO (1) | WO1998031775A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11142352B2 (en) | 2016-07-18 | 2021-10-12 | Azurity Pharmaceuticals, Inc. | Apparatus and method for filling bulk materials into a container |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19944218A1 (de) * | 1999-09-15 | 2001-03-29 | Cognis Deutschland Gmbh | Waschmitteltabletten |
DE19956802A1 (de) * | 1999-11-25 | 2001-06-13 | Cognis Deutschland Gmbh | Waschmitteltabletten |
DE19956803A1 (de) * | 1999-11-25 | 2001-06-13 | Cognis Deutschland Gmbh | Tensidgranulate mit verbesserter Auflösegeschwindigkeit |
EP1201741A1 (de) * | 2000-10-31 | 2002-05-02 | The Procter & Gamble Company | Waschmittelzusammensetzungen |
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 |
CN102414305B (zh) * | 2009-04-24 | 2014-07-23 | 荷兰联合利华有限公司 | 高活性洗涤剂颗粒的制备 |
DE102010055741A1 (de) * | 2010-12-22 | 2012-06-28 | Clariant International Ltd. | Zusammensetzungen enthaltend sekundäres Paraffinsulfonat und Tetrahydroxypropylethylendiamin |
DE102010055743A1 (de) * | 2010-12-22 | 2012-06-28 | Clariant International Ltd. | Zusammensetzungen enthaltend sekundäres Paraffinsulfonat und Alkoholalkoxylat |
DE102010055742A1 (de) * | 2010-12-22 | 2012-06-28 | Clariant International Ltd. | Zusammensetzungen enthaltend sekundäres Paraffinsulfonat und Alkoholalkoxylat |
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 |
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 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL200200A (de) * | 1954-09-06 | |||
DE2415159A1 (de) * | 1974-03-29 | 1975-10-09 | Hoechst Ag | Alkalialkansulfonathaltige spruehprodukte und verfahren zu ihrer herstellung |
DE2423391C2 (de) * | 1974-05-14 | 1983-08-04 | Hoechst Ag, 6230 Frankfurt | Waschmittel |
ZA807664B (en) * | 1979-12-14 | 1982-07-28 | Unilever Ltd | Process for making detergent compositions |
DE3104371A1 (de) * | 1981-02-07 | 1982-11-11 | Henkel KGaA, 4000 Düsseldorf | "reinigungsmitteltablette" |
JPH0726120B2 (ja) * | 1988-03-10 | 1995-03-22 | 株式会社ジャパンエナジー | 洗剤組成物 |
JPH0310000A (ja) * | 1989-06-07 | 1991-01-17 | Nippon Mining Co Ltd | 洗剤用組成物 |
DE4001247A1 (de) * | 1990-01-18 | 1991-07-25 | Bayer Ag | Verfahren zur verbesserung der fliessfaehigkeit von dimerisiertem 2,4-toluylendiisocyanat |
AU7361594A (en) * | 1993-07-14 | 1995-02-13 | Procter & Gamble Company, The | Percarbonate bleach particles coated with a partially hydrated crystalline aluminosilicate flow aid |
JPH0764317A (ja) * | 1993-08-24 | 1995-03-10 | Ricoh Co Ltd | 静電荷像現像用トナー |
FR2721616A1 (fr) * | 1994-06-22 | 1995-12-29 | Hoechst France | Compositions de tensioactifs anioniques en poudre, en perles ou en granulés, leur procédé de préparation et leur utilisation dans les produits de nettoyage et d'entretien. |
-
1997
- 1997-01-21 DE DE19701896A patent/DE19701896A1/de not_active Withdrawn
-
1998
- 1998-01-09 AU AU62921/98A patent/AU6292198A/en not_active Abandoned
- 1998-01-09 JP JP53362998A patent/JP4263246B2/ja not_active Expired - Fee Related
- 1998-01-09 EP EP98906864A patent/EP0966510B1/de not_active Expired - Lifetime
- 1998-01-09 DE DE59809971T patent/DE59809971D1/de not_active Expired - Lifetime
- 1998-01-09 WO PCT/EP1998/000089 patent/WO1998031775A1/de active IP Right Grant
- 1998-01-09 ES ES98906864T patent/ES2210725T3/es not_active Expired - Lifetime
- 1998-01-19 AR ARP980100219A patent/AR011543A1/es unknown
- 1998-01-20 US US09/009,229 patent/US6051544A/en not_active Expired - Lifetime
-
2008
- 2008-07-25 JP JP2008191737A patent/JP5124379B2/ja not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9831775A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11142352B2 (en) | 2016-07-18 | 2021-10-12 | Azurity Pharmaceuticals, Inc. | Apparatus and method for filling bulk materials into a container |
Also Published As
Publication number | Publication date |
---|---|
DE19701896A1 (de) | 1998-07-23 |
US6051544A (en) | 2000-04-18 |
AU6292198A (en) | 1998-08-07 |
AR011543A1 (es) | 2000-08-30 |
EP0966510B1 (de) | 2003-10-22 |
DE59809971D1 (de) | 2003-11-27 |
JP5124379B2 (ja) | 2013-01-23 |
JP4263246B2 (ja) | 2009-05-13 |
JP2008285683A (ja) | 2008-11-27 |
WO1998031775A1 (de) | 1998-07-23 |
ES2210725T3 (es) | 2004-07-01 |
JP2001508118A (ja) | 2001-06-19 |
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