EP2262882B1 - Procédé pour produire des sels de métal alcalino-terreux solides d acides paraffine-sulfoniques secondaires - Google Patents

Procédé pour produire des sels de métal alcalino-terreux solides d acides paraffine-sulfoniques secondaires Download PDF

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Publication number
EP2262882B1
EP2262882B1 EP09720746A EP09720746A EP2262882B1 EP 2262882 B1 EP2262882 B1 EP 2262882B1 EP 09720746 A EP09720746 A EP 09720746A EP 09720746 A EP09720746 A EP 09720746A EP 2262882 B1 EP2262882 B1 EP 2262882B1
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Prior art keywords
acid
acids
alkaline earth
earth metal
salts
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German (de)
English (en)
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EP2262882A1 (fr
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Gerd Reinhardt
Peter Naumann
Georg Borchers
Mathias Groeschen
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Clariant Finance BVI Ltd
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Clariant Finance BVI Ltd
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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
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying

Definitions

  • the present invention relates to the synthesis of solid alkaline earth metal salts of secondary paraffin sulfonic acids. Furthermore, the present invention relates to solid detergents and cleaners containing such alkaline earth metal salts of secondary paraffin sulfonic acids.
  • paraffin sulfonic acids are (s ek. A lkansulfon s äuren, SAS) used in the form of sodium salts in the liquid detergent and cleaning agent formulations.
  • These sodium salts of secondary paraffin sulfonic acid have an extremely high hygroscopicity, whereby a simple isolation and later handling are made very difficult or even impossible.
  • the hygroscopic Na salts are used in solid detergent formulations (eg washing powders), amounts added above about 5%, adhesions and lumps in the end product, which severely limits their field of application.
  • Example 1 liquid detergents and cleaners containing surfactant mixtures of semi-polar nonionic surfactants and anionic surfactants.
  • anionic surfactants alkaline earth metal salts of anionic surfactants are used, wherein as anionic surfactant and paraffin sulfonate is called.
  • no pure alkaline earth metal salt of paraffin-sulfonic acids is disclosed there, but merely their mixture with other surfactants. This is due to the manufacturing process in which a mixture of nonionic and anionic surfactants in the acid form is neutralized. Subsequently, a soluble alkaline earth metal salt is added. Solid, powdered alkaline earth salts sec. Alkanesulfonic acids in pure form are not described.
  • the object of the invention was therefore to produce alkaline earth metal salts of secondary Paraffinsulfonklaren in pure form. This object has been achieved by subjecting an aqueous solution of paraffin sulfonic acid and alkaline earth metal hydroxide to spray drying.
  • the invention thus provides a process for the preparation of solid alkaline earth metal salts of sec. Paraffin sulfonic acids, in which an aqueous solution of a paraffin sulfonic acid and an alkaline earth metal salt is converted by spray drying into a solid form.
  • Paraffin-sulfonic acids are known per se. They generally have a chain length of 7 to 20, preferably 8 to 18 carbon atoms. Due to the different valence of alkaline earth metal cation and sec. Paraffinsulfonic acid can form two different salts in the ratio M 2+ to paraffin-sulfonic acid, which can be represented by formulas with M (SAS) 2 or M (OH) SAS, where M is the alkaline earth metal cation and SAS is the paraffin sulfonic acid.
  • the paraffin-sulfonic acids used as starting compounds can be isolated either by distillation or solvent extraction with lower “alcohols” or with supercritical CO 2 from sulfoxidation mixtures of longer-chain alkanes. If necessary, the paraffin sulfonic acids can be bleached with 30, 50 or 70% hydrogen peroxide prior to neutralization.
  • the paraffin sulphonic acids usually have an active ingredient concentration of 70 to 99%, preferably from 80 to 95%, particularly preferably from 85 to 95%.
  • the amount of 30% hydrogen peroxide required for bleaching is about 1 to 5% by weight, preferably 2 to 3% by weight, based on the paraffin sulfonic acid used.
  • the bleaching is carried out at 10 to 30 ° C, preferably at 15 to 25 ° C, the bleaching time is 2 to 6 hours, preferably 3 to 5 hours.
  • the resulting Mg (SAS) 2 has a pH in the acidic range (pH 2-4). This product may then be adjusted to a neutral pH with a little sodium hydroxide or sodium carbonate, if necessary.
  • Mg (OH) SAS has a pH of 6 to 9.
  • the aqueous solution of the salt thus produced is converted by removal of the water, by spray drying in the solid powdery Erdalkamimetall-Paraffinsulfonat.
  • Spray drying processes are well known to those skilled in the art and can typically be carried out in spray towers but also fluidized bed apparatuses.
  • the material to be dried is sprayed in the form of an aqueous solution or slurry at the top of the spray tower.
  • a spray liquid with favorable properties for the process, such.
  • viscosity, distribution of solids in a suspension it may be necessary to treat the liquid accordingly and / or add suitable auxiliaries.
  • the treatment of the spray can z. B. by a temperature control or include the passage of a homogenization step.
  • the distribution of solids in a spray slurry or the surface tension can be influenced.
  • various systems are available, such as single, dual or multi-substance nozzles or atomizer disks, with which fine liquid droplets are produced.
  • the drying is carried out by hot gas, which is passed in cocurrent or countercurrent to the direction of spray through the tower.
  • the dried particles are separated from the gas stream after the dryer, usually with the help of cyclones and / or dust filters.
  • the drying process is primarily determined by the temperature profile of the inlet and outlet temperatures. Care must be taken to ensure that, on the one hand, the inlet temperature is not too high and the outlet temperature is not too low.
  • alkaline earth metal salts of paraffin sulfonic acids produced in this way are characterized by the lowest possible hygroscopicity. This makes them easier to package into a solid dosage form and easier to incorporate into solid washing and cleaning formulations. It is also possible to formulate these salts in the form of powders, granules or co-granules with other, preferably solid, surfactants.
  • the alkaline earth metal salts of secondary paraffin sulfonic acids can be used both in detergents and cleaners, both with and without the use of a carrier.
  • the spray-dried alkaline earth metal salts of secondary paraffin sulfonic acids obtained according to the invention are suitable directly for use in detergents and cleaners. In a particularly preferred form of use, however, they can first be granulated by processes known per se and then provided with a coating shell. For granulation are in Principle all common methods conceivable, such. As compaction, build-up and mixer granulation, fluidized bed granulation, extrusion or pelletizing. Depending on the requirements of the end product and / or the granulation process, the use of auxiliaries, additives, other active components, etc. may be required.
  • the granules are coated in an additional step with a film-forming substance, whereby the product properties can be significantly influenced or specifically adjusted.
  • the coating agent is applied in the form of a solution or a melt, in special cases as a solid.
  • Common processes in this case are the fluidized bed or suitable mixers, which are operated depending on the requirements with a subsequent drying or cooling. In principle, methods for micro- or matrix encapsulation are also conceivable.
  • the spray powders obtained according to the invention are distinguished by a very good storage stability in pulverulent washing, cleaning and washing
  • Disinfectant formulations from. They are ideal for use in heavy-duty detergents, stain salts, toilet blocks and other shaped articles, machine dishwashing detergents and powdery all-purpose cleaners.
  • the alkaline earth metal salts of secondary paraffin sulfonic acids are used in the detergents and cleaners in concentrations of 1 to 60%, preferably 2 to 30% and in particular 3 to 15%.
  • the detergents and cleaners which may be in the form of granules, powdered or tablet-form solids, and other shaped articles, may contain, in addition to the alkaline earth metal salts of secondary paraffin sulfonic acids, in principle all known and conventional ingredients in such agents.
  • the detergents and cleaners may in particular be further surface-active surfactants, peroxygen compounds, peroxygen activators or organic peracids, builders, inorganic and organic acids, bases, Cleaning enhancers, solvents, hydrotropes, buffers, complexing agents, preservatives, thickeners, skin protection agents, foam regulators, disinfectants, enzymes and special additives with color or fiber-sparing effect included.
  • Other excipients such as electrolytes and dyes and perfumes are possible.
  • a hard surface cleaner can contain abrasive components, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres, and mixtures thereof.
  • Abrasives are preferably not more than 20 wt .-%, in particular from 5 to 15 wt .-%, contained in the cleaning agents according to the invention.
  • the detergents and cleaners may contain one or more further surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, as well as cationic, zwitterionic and amphoteric surfactants.
  • Such surfactants are present in detergent compositions according to the invention in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas in hard-surface cleaners normally lower proportions, that is to say amounts of up to 20% by weight. , in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included.
  • suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • surfactants of the sulfonate preferably C 8 -C 18 alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis the sulfonation obtained.
  • alkanesulfonates prepared from C 12 -C 18 alkanes, for example by sulfochlorination with subsequent hydrolysis or neutralization be won.
  • esters of alpha-sulfo fatty acids for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.
  • alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -C 20 -oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) ylsulfates of said chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
  • sulfuric acid monoesters of straight-chain or branched alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -fatty alcohols with 1 up to 4 EO.
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol residues or mixtures of these.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate).
  • anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and Behenic acid and in particular from natural fatty acids, such as coconut, palm kernel or tallow, derived soap mixtures derived.
  • the anionic surfactants including the soaps, present in addition to the alkaline earth metal salts of secondary paraffinic acids according to the invention may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 50% by weight and in particular in amounts of from 5 to 25% by weight.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position , or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl polyglycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and 6 for a Glycoside unit with 5 or 6 C-atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) where R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-alyloxy-substituted compounds can then be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettklaamide.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and the fatty acid alkanolamides may also be suitable.
  • surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides. Other surfactant types may have dendrimeric structures.
  • Suitable peroxidic bleaches are hydrogen peroxide and under the washing and cleaning conditions hydrogen peroxide donating compounds such as alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts and inorganic persalts such as alkali metal perborates, percarbonates, perphosphates, persilicates, persulfates and peroxynitrite. Mixtures of two or more of these compounds are also suitable. Particularly preferred are sodium perborate tetrahydrate and in particular sodium perborate monohydrate and sodium percarbonate. Sodium perborate monohydrate is preferred for its good storage stability and good solubility in water. Sodium percarbonate may be preferred for environmental reasons.
  • Hydroperoxides are another suitable group of peroxide compounds. Examples of these substances are cumene hydroperoxide and t-butyl hydroperoxide.
  • Aliphatic or aromatic mono- or dipercarboxylic acids and the corresponding salts are suitable as peroxy compounds.
  • examples include peroxynaphthoic acid, peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid (PAP), 1,12-diperoxydodecanedioic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-diacid and 4,4'-sulfonyl -bisperoxybenzoeklare.
  • PAP N-phthaloylaminoperoxycaproic acid
  • 1,12-diperoxydodecanedioic acid 1,9-diperoxyazelaic acid
  • diperoxysebacic acid diperoxyisophthalic acid
  • the detergents and cleaners may also contain suitable bleach activators in the usual amounts (about 1 to 10% by weight).
  • Suitable bleach activators are organic compounds having an O-acyl or N-acyl group, in particular from the group of the activated carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate, sodium 4-benzoyloxy-benzenesulfonate, sodium trimethylhexanoyloxy-benzenesulfonate, Carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, lactones, acylals, carboxylic acid amides, acylated ureas and oxamides, N-acylated hydantoins, for example 1-phenyl-3-acetylhydantoin , Hydrazides, triazoles, hydrotriazines,
  • sulfonimines open chain or cyclic quaternary iminium compounds such as dihydroisoquinolinium quats or dihydroisoquinolinium betaines and / or bleach-enhancing transition metal salts, or mono- or polynuclear transition metal complexes having acyclic or macrocyclic ligands can also be included.
  • Suitable organic and inorganic builders are neutral or in particular alkaline salts which precipitate or complex calcium ions.
  • Suitable and particularly ecologically harmless builders are crystalline, layered silicates of the general formula NaMSi (x) O (2x + 1) , where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4 and y is a number from 0 to 33, for example Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5 , natrosilite), Na-SKS -9 (NaHSi 2 O 5 * H 2 O), Na-SKS-10 (NaHSi 2 O 3 * 3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5) and Na-SKS NaHSi 2 O 5 ), but especially Na-SKS-6 ( ⁇ -Na 2 Si 2 O 5 ) and fine-crystalline, synthetic hydrous zeolites, in particular of the Na
  • Zeolites and phyllosilicates may be included in an amount of up to 60% by weight on average.
  • non-neutralized or partially neutralized (co) polymeric polycarboxylic acids are suitable. These include the homopolymers of acrylic acid or methacrylic acid or their copolymers with other ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, ethylacrylic acid, vinylacetic acid, allylacetic acid, maleic acid, fumaric acid, itaconic acid, meth (allylsulfonic acid), vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid and phosphorous groups Monomers such as vinylphosphoric acid, allylphosphoric acid and acrylamidomethylpropanephosphoric acid and their salts, and hydroxyethyl (meth) acrylate sulfate, allyl alcohol sulfate and allyl alcohol phosphates.
  • ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid
  • Preferred (co) polymers have an average molecular weight of from 1,000 to 100,000 g / mol, preferably from 2,000 to 75,000 g / mol and in particular from 2,000 to 35,000 g / mol.
  • the degree of neutralization of the acid groups is advantageously from 0 to 90%, preferably from 10 to 80% and in particular from 30 to 70%.
  • Particularly suitable polymers include homopolymers of acrylic acid and copolymers of (meth) acrylic acid with maleic acid or maleic anhydride.
  • copolymers are derived from terpolymers which are obtained by polymerization of 10 to 70 wt .-% of monoethylenically unsaturated dicarboxylic acids having 4 to 8 carbon atoms, their salts, 20 to 85 wt .-% monoethylenically unsaturated monocarboxylic acids having 3 to 10 C -Atoms or their salts, 1 to 50 wt .-% of monounsaturated monomers which release after hydrolysis hydroxyl groups on the polymer chain, and 0 to 10 wt .-% of other free-radically copolymerizable monomers.
  • graft polymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides and animal or vegetable proteins are also suitable.
  • polyspartic acid or its derivatives in non-neutralized or only partially neutralized form.
  • graft polymers of acrylic acid, methacrylic acid, maleic acid and other ethylenically unsaturated monomers to salts of polyaspartic acid, as usually obtained in the hydrolysis of the polysuccinimide described above. This can be dispensed with the otherwise necessary addition of acid for the preparation of only partially neutralized form of polyaspartic acid.
  • the amount of polyaspartate is usually chosen so that the degree of neutralization of all incorporated in the polymer carboxyl groups does not exceed 80%, preferably 60%.
  • carboxylic acids preferably used in the form of their sodium salts, such as citric acid, in particular trisodium citrate and trisodium citrate dihydrate, nitrilotriacetic acid and their water-soluble salts; the alkali metal salts of carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid, gluconic acid, mellitic acid, benzopolycarboxylic acids and those as in U.S. Patent 4,144,226 and 4 146 495 disclosed.
  • their sodium salts such as citric acid, in particular trisodium citrate and trisodium citrate dihydrate, nitrilotriacetic acid and their water-soluble salts
  • Phosphate-containing builders for example alkali phosphates, which may be present in the form of their alkaline neutral or acidic sodium or potassium salts are also suitable.
  • Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with oligomerization amounts in the range of 5 to 1,000, in particular 5 to 50, and mixtures of sodium and potassium salts.
  • These builders may be contained from 5 to 80 wt .-%, preferably a proportion of 10 to 60 wt .-%.
  • chelating agents such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can be used.
  • compositions according to the invention may contain volatile alkalizing compounds. These include ammonia and / or C 1-9 alkanolamines. As alkanolamines, ethanolamines are preferred, especially preferred is monoethanolamine.
  • Detergents may further contain organic acids such as acetic acid, glycolic acid, lactic acid, citric acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid, preferred are acetic acid, citric acid and lactic acid, particularly preferred is acetic acid.
  • organic acids such as acetic acid, glycolic acid, lactic acid, citric acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid, preferred are acetic acid, citric acid and lactic acid, particularly preferred is acetic acid.
  • Acid detergent formulations according to the invention may in particular be inorganic acids, for example mineral acids such as phosphoric acid, sulfuric acid, nitric acid or hydrochloric acid, but also sulfamic acid.
  • organic acids preferably short-chain aliphatic mono-, di- and tricarboxylic acids, hydroxycarboxylic acids and dicarboxylic acids.
  • aliphatic monocarboxylic acids and dicarboxylic acids are C 1 -C 6 -alkyl and -alkenyl acids, such as glutaric acid, succinic acid, propionic acid, adipic acid, maleic acid, formic acid and acetic acid.
  • hydroxycarboxylic acids may be mentioned hydroxyacetic acid and citric acid.
  • sulfonic acids of the formula R-SO 3 H which contain a straight-chain or branched and / or cyclic or unsaturated C 1 -C 32 -hydrocarbon radical R, for example C 6-22 -alkanesulfonic acids, C 6-22 - ⁇ -alkanesulfonic acids, C 6 22 - ⁇ -olefinsulfonic acids and C 122 -alkyl-C 6-10 -arylsulfonic such.
  • R-SO 3 H which contain a straight-chain or branched and / or cyclic or unsaturated C 1 -C 32 -hydrocarbon radical R, for example C 6-22 -alkanesulfonic acids, C 6-22 - ⁇ -alkanesulfonic acids, C 6 22 - ⁇ -olefinsulfonic acids and C 122 -alkyl-C 6-10 -arylsulfonic such.
  • C 1-22 -alkylbenzenesulfonic acids or C 1-22 -alkylnaphthalenesulfonic acids, preferably C 8-16 linear alkylbenzenesulfonic acids, can be used.
  • Particularly preferred are citric acid, acetic acid, formic acid and amidosulfonic acid.
  • Alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used.
  • Further preferred alcohols are polyethylene glycols having a molecular weight below 2,000. In particular, use of polyethylene glycol having a molecular weight of between 200 and 600 and in amounts of up to 45% by weight and of polyethylene glycol having a molecular weight of between 400 and 600 in amounts of from 5 to 25% by weight is preferred.
  • An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1.
  • Suitable solvents include triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
  • Preferred thickeners are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of from 0 to 5% by weight and in particular in amounts of from 0.5 to 2% by weight, for example sodium, potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and polysaccharides, in particular xanthan gum, guar-guar, agar-agar, alginates and tyloses, carboxymethylcellulose and hydroxyethylcellulose, furthermore higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, Polyvinyl alcohol and polyvinylpyrrolidone and electrolytes such as sodium chloride and ammonium chloride used.
  • Suitable thickeners are water-soluble polyacrylates which are, for example, cross-linked with about 1% of a polyallyl ether of sucrose and which have a relative molecular mass of more than one million. Examples are the polymers obtainable under the name Carbopol ® 940 and 941st The cross-linked Polyacrylates are used in amounts of not more than 1% by weight, preferably in amounts of from 0.2 to 0.7% by weight.
  • enzymes include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP ®, Optimase ®, Opticlean ®, Maxacal ®, Maxapem ®, Durazym ®, Purafect ® OxP, Esperase ® and / or Savinase ®, amylases as Termamy ®, amylase LT, Maxamyl ®, Duramyl ®, Purafectel OxAm, cellulases as Celluzyme ®, Carezyme ®, K-AC ® and / or from the international patent applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase ®, Lipomax ®, Lumafast ® and / or Lipozym ®.
  • proteases such as BLAP ®, Optimase ®
  • the enzymes used can, for example, in the international patent applications WO 92/111 347 or WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in the detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation being used.
  • Machine dishwashing detergents according to the invention preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates may be present in amounts of up to 40% by weight. in particular from 3 to 30% by weight, based on the total agent.
  • the alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.
  • inventive means for automatically cleaning dishes are 20 to 60 wt .-% water-soluble organic Builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes.
  • the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • a foam-regulating compound preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • the foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • Further optional ingredients in the compositions according to the invention are, for example, perfume oils.
  • Suitable salts or setting agents are, for example, sodium sulfate, sodium carbonate or sodium silicate (water glass).
  • the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions according to the invention.
  • compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations and other shaped articles which are known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes , Bleaching agent and the bleach catalyst are to be expected, can be prepared.
  • compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l can also be achieved by increasing the builder components with at least a proportion of liquid mixture components in a first process stage the bulk density of this premix is mixed and subsequently - if desired, after an intermediate drying - the other constituents of the agent, including the cationic nitrile activator combined with the thus obtained premix.
  • compositions according to the invention in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture is compressed by means of conventional tablet presses, for example Exzeriterpressen or rotary presses.
  • a tablet produced in this way has a weight of 1.5 g 40 g, in particular from 20 g to 30 g; at a diameter of 3-5 mm to 40 mm.
  • a further preferred embodiment comprises lumpy preparations which can be used for improving odor and cleaning in toilet bowls (so-called toilet blocks) containing, in addition to the alkaline earth metal salts of secondary paraffinic according to the invention further 15 to 30 wt .-% of anionic and / or nonionic surfactants, preferably fatty alkyl sulfates, alkylbenzenesulfonates , Alkyl polyglucosides, fatty alkyl ether sulfates, fatty alkyl ethoxylates, 10 to 40 wt .-% organic solvent, 5 to 15 wt .-% of one or more acids or salts thereof, for.
  • anionic and / or nonionic surfactants preferably fatty alkyl sulfates, alkylbenzenesulfonates , Alkyl polyglucosides, fatty alkyl ether sulfates, fatty alkyl ethoxylates, 10 to 40 wt
  • formic acid acetic acid, sulfamic acid, sodium hydrogen sulfate, coconut fatty acids, 0 to 5 wt .-% complexing agent, eg.
  • sodium citrate or sodium phosphonate 0 to 60 wt .-% builders, for.
  • sodium sulfate and 0 to 5 wt .-% colorants 0 to 5 wt .-% colorants, fragrances and disinfectants and water.
  • a further preferred embodiment involves pulverulent formulations which can be used to purify toilets (so-called WC powder containing, in addition to the alkaline earth metal salts of secondary paraffin sulfonic acids according to the invention, a further 15 to 30% by weight of anionic and / or nonionic surfactants Fatty alkyl sulfates, fatty alkyl ethoxylates, alkylbenzenesulfonates, alkylpolyglucosides, fatty alkyl ether sulfates, 10 to 50% by weight of acid, preferably formic acid, acetic acid, citric acid, sulfamic acid, potassium or sodium hydrogen sulfate, 0 to 5% by weight of complexing agent, 0 to 10% by weight of auxiliary - And fillers, preferably sodium carbonate, 0 to 5 wt .-% colorants, fragrances and disinfectants and water.
  • anionic and / or nonionic surfactants Fatty alkyl sul
  • pieces of detergent in block or tablet form which are used for cleaning and rinsing of solid surfaces such.
  • tableware floors, windows but also textiles can be used, containing in addition to the alkaline earth metal salts according to the invention secondary paraffin sulfonic another 0 to 25 wt .-% of anionic and / or nonionic surfactants, preferably fatty alkyl sulfates, Alkylbenzenesulfonates, alkylpolyglucosides, fatty alkyl ether sulfates, betaines, amine oxides, alpha-olefinsulfonates, 10 to 40% by weight of organic solvent, 0 to 5% by weight of colorants, fragrances and disinfectants, and water.
  • anionic and / or nonionic surfactants preferably fatty alkyl sulfates, Alkylbenzenesulfonates, alkylpolyglucosides, fatty alkyl ether sulfates, betaines,
  • the detergents and cleaners may contain any of the conventional additives in amounts commonly found in such compositions.
  • magnesium paraffin sulfonate powder thus obtained proved to be insensitive. Despite some water absorption, the material remained mechanically stable and after completion of the test was a dry, free-flowing powder.
  • a 30% aqueous solution of Natriumparaffinsulfonats was used, prepared by diluting a 60% goods (Hostapur SAS 60 - commercial product Clariant).

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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)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

  1. Procédé de fabrication de sels de métaux alcalino-terreux solides d'acides paraffine-sulfoniques secondaires, caractérisé en ce qu'une solution aqueuse d'un acide paraffine-sulfonique secondaire et d'un hydroxyde de métal alcalino-terreux est transformée en une forme solide par séchage par pulvérisation.
  2. Procédé selon la revendication 1, caractérisé en ce qu'un acide paraffine-sulfonique secondaire contenant 7 à 20 atomes C est utilisé.
  3. Procédé selon la revendication 1, caractérisé en ce que l'acide paraffine-sulfonique secondaire utilisé a une concentration d'agent actif de 70 à 99 %.
  4. Procédé selon la revendication 1, caractérisé en ce que l'acide paraffine-sulfonique secondaire utilisé a une concentration d'agent actif de 85 à 95 %.
  5. Procédé selon la revendication 1, caractérisé en ce que l'acide paraffine-sulfonique secondaire est blanchi avec l'hydroxyde de métal alcalino-terreux avant la réaction.
  6. Procédé selon la revendication 1, caractérisé en ce que le rapport molaire entre l'acide paraffine-sulfonique secondaire et l'hydroxyde de métal alcalino-terreux est de 0,8 à 2,5.
  7. Procédé selon la revendication 1, caractérisé en ce que le rapport molaire entre l'acide paraffine-sulfonique secondaire et l'hydroxyde de métal alcalino-terreux est de 1,0 à 2,0.
EP09720746A 2008-03-11 2009-03-04 Procédé pour produire des sels de métal alcalino-terreux solides d acides paraffine-sulfoniques secondaires Not-in-force EP2262882B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008013606A DE102008013606A1 (de) 2008-03-11 2008-03-11 Verfahren zur Herstellung fester Erdalkalimetallsalze sekundärer Paraffinsulfonsäuren
PCT/EP2009/001512 WO2009112187A1 (fr) 2008-03-11 2009-03-04 Procédé pour produire des sels de métal alcalino-terreux solides d’acides paraffine-sulfoniques secondaires

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EP2262882A1 EP2262882A1 (fr) 2010-12-22
EP2262882B1 true EP2262882B1 (fr) 2012-12-12

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US (1) US8426635B2 (fr)
EP (1) EP2262882B1 (fr)
JP (1) JP5559706B2 (fr)
DE (1) DE102008013606A1 (fr)
ES (1) ES2396480T3 (fr)
WO (1) WO2009112187A1 (fr)

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JP6258210B2 (ja) 2012-09-27 2018-01-10 テルモ株式会社 生検デバイス
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
US10646607B2 (en) 2014-09-17 2020-05-12 Lonza, Inc. Activated disinfectant hydrogen peroxide compositions

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US20110021812A1 (en) 2011-01-27
JP5559706B2 (ja) 2014-07-23
US8426635B2 (en) 2013-04-23
ES2396480T3 (es) 2013-02-21
EP2262882A1 (fr) 2010-12-22
DE102008013606A1 (de) 2009-09-17
JP2011514905A (ja) 2011-05-12
WO2009112187A1 (fr) 2009-09-17

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