EP1237893A1 - Procede de production de pates d'(ether)sulfate de magnesium - Google Patents

Procede de production de pates d'(ether)sulfate de magnesium

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Publication number
EP1237893A1
EP1237893A1 EP00989946A EP00989946A EP1237893A1 EP 1237893 A1 EP1237893 A1 EP 1237893A1 EP 00989946 A EP00989946 A EP 00989946A EP 00989946 A EP00989946 A EP 00989946A EP 1237893 A1 EP1237893 A1 EP 1237893A1
Authority
EP
European Patent Office
Prior art keywords
acid
magnesium
alcohol
fatty
oil
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.)
Withdrawn
Application number
EP00989946A
Other languages
German (de)
English (en)
Inventor
Michael Neuss
Karl Heinz Schmid
Michael Langen
Christoph Breucker
Hans-Dieter Schraven
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1237893A1 publication Critical patent/EP1237893A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • 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
    • C11D1/146—Sulfuric acid esters

Definitions

  • the invention relates to magnesium (ether) sulfate pastes with an active substance content of at least 30% by weight, a process for the preparation of these pastes and their use in surface-active preparations.
  • Surface-active preparations in particular those used in the field of detergents and cleaning agents and in personal care, usually contain anionic surfactants, such as, for example, alkyl (ether) sulfates. These are of great importance because of their strong cleaning performance and their pronounced foaming power, for example in manual dishwashing detergents or hair shampoos. With regard to skin tolerance, the magnesium (ether) sulfates are particularly noteworthy. These magnesium salts of alkyl sulfates and alkyl ether sulfates are usually only offered in the form of a dilute solution with a solids content of about 30% by weight. The reason for this is the problematic handling of the magnesium base, which is used to neutralize the acidic sulfation product.
  • anionic surfactants such as, for example, alkyl (ether) sulfates.
  • the usual diluted magnesium (ether) sulfate solutions are prepared according to the current state of the art in such a way that the acidic ester to be neutralized - coming from the sulfation - directly into an aqueous slurry of the magnesium base (usually magnesium oxide or hydroxide) is driven in.
  • the magnesium base usually magnesium oxide or hydroxide
  • the object of the present invention was to provide a process for the production of magnesium (ether) sulfates with a solids content of above 30% by weight, in which they are in the form of pastes and with little technical effort are accessible.
  • these magnesium (ether) sulfate pastes should have good emulsifier properties and be suitable for the preparation of surface-active preparations. Description of the invention
  • the invention relates to magnesium (ether) sulfate pastes with a solids content of at least 30, preferably 50 to 80 and in particular 55 to 80% by weight, obtainable by Sulfated fatty alcohols and / or fatty alcohol ethoxylates, (II) the resulting sulfation product - preferably with vigorous stirring - mixed with an aqueous slurry of magnesium base, in particular a combination of magnesium base and an alkali base, (III) then added to the resulting paste
  • Magnesium base contained - preferably with intensive stirring - by adding an acid, preferably an inorganic acid and in particular a combination of an inorganic and an organic acid to a pH of 2 to 5 neutralized (IV) and ultimately with bases - preferably under intensive stirring - adjusted to a pH below 7.
  • Another object of the invention is a process for the preparation of magnesium (ether) sulfate pastes, which is characterized in that (I) sulfated fatty alcohols and / or fatty alcohol ethoxylates, (II) the resulting sulfation product - preferably with intensive stirring - with a aqueous slurry of magnesium base, in particular a combination of magnesium base and an alkali base, (III) then the magnesium base still contained in the resulting paste - preferably with intensive stirring - by adding an acid, preferably an inorganic acid, in particular a combination of an inorganic and an organic acid is neutralized to a pH of 2 to 5 (IV) and ultimately - preferably with intensive stirring - adjusted to a pH below 7 with bases.
  • an acid preferably an inorganic acid, in particular a combination of an inorganic and an organic acid
  • magnesium (ether) sulfate pastes with a solids content above 30% by weight can be produced simply, quickly and cheaply using the process according to the invention.
  • these pastes have good emulsifier properties and are suitable for the production of surface-active preparations.
  • fatty alcohols that are suitable as starting materials, primary aliphatic alcohols are the
  • R 1 represents an aliphatic, linear or branched hydrocarbon radical having 6 to 22 carbon atoms and 0 and / or 1, 2 or 3 double bonds.
  • Typical examples are capronic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroseyl alcohol, linoleyl alcohol, linolenyl alcohol, linolenyl alcohol, linoleyl alcohol , Erucyl alcohol and brassidyl alcohol and their technical mixtures, which are used, for example, in the high-pressure hydrogenation of technical methyl esters based on fats and oils or aldehydes from Roelen's oxosynthesis and as a monomer fraction in the dimerization of unsaturated fatty alcohols
  • R 2 is a linear or branched, saturated or unsaturated hydrocarbon radical having 6 to 22, preferably 10 to 18 and in particular 12 to 14 carbon atoms and m for numbers of 1 to 10 on average; is preferably 2 to 5.
  • Typical examples are addition products of 1 to 10 ethylene oxide units with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol, elaol alcohol,
  • the sulfonation can be carried out using the processes known from the prior art for producing alkyl (ether) sulfates; the production processes using gaseous sulfur trioxide or chlorosulfonic acid, in particular gaseous sulfur trioxide, are preferred.
  • Fatty alcohols and / or fatty alcohol ethoxylates were placed in a tubular reactor at preferably 30 to 50 ° C. In the case of the mixtures, a weight ratio of fatty alcohol: fatty alcohol ethoxylate is selected in the range from 20:80 to 80:20, preferably 20:60 to 60:40 and in particular 30:70 to 40:60. Gaseous sulfur trioxide was introduced into this mixture.
  • the crude sulfation product was then treated with an aqueous slurry of magnesium base, preferably magnesium oxide and / or magnesium hydroxide, or with an aqueous slurry of a combination of 10 to 50, preferably 20 to 40 and in particular 25 to 35% by weight the final concentration the aqueous slurry - magnesium base, preferably magnesium oxide, and 0.1 to 15, preferably 2 to 5% by weight - based on the final concentration of the aqueous slurry - neutralized with alkali metal hydroxide solution, preferably sodium hydroxide solution.
  • the resulting mixture was in the form of a flowable, alkaline paste with a pH (3%) of 8 to 12, preferably 9 to 11.
  • the raw sulfation product was - preferably with intensive stirring - collected in a confectioning tank with a conventional stirrer (eg cross-bar stirrer) and preferably for more intensive stirring with a combination of the usual stirrer in the confectioning tank and an additional homogenizer (intensive mixer);
  • the packaging container was provided with a bypass, through which the paste was pumped upwards back into the container from the lower region of the container via a homogenizer (intensive stirrer).
  • the excess magnesium oxide was brought up to a pH (3% by weight) using a 10 to 50, preferably 10 to 30% by weight inorganic acid, preferably sulfuric acid.
  • the majority of the excess magnesium oxide was dissolved at 30 to 60 ° C., preferably 40 to 50 ° C., using a 10 to 50, preferably 10 to 30% by weight inorganic acid, preferably sulfuric acid; the resulting pH was (3% by weight) 7 to 10 and preferably 8 to 9.
  • the organic acid preferably lactic acid, citric acid and / or acetic acid and in particular lactic acid, was then added, resulting in a pH value (3% by weight) from 2 to 5 and preferably 3 to 4. This was held to dissolve the remaining magnesium oxide over a period of 1 to 24, preferably 6 to 12 hours at 30 to 60 ° C. and preferably 40 to 50 ° C. Acidification using only organic acids is possible in principle, but is not practical in practice for economic reasons and because of the high amounts of salts that are formed.
  • Magnesium (ether) sulfate pastes produced in this way have, as typical indicators, active substance (Epton): 50 to 75%, preferably 55 to 70%; Unsulfated content: 1 to 10%, preferably 3 to 7%; Water content: 20 to 40%, preferably 25 to 35%; Sulphate content: max. 5%, preferably 1 to 3%.
  • the content of magnesium salts of the alkyl (ether) sulfates according to the invention should be greater than 60%, preferably greater than 80%, in particular greater than 90%.
  • the alkyl (ether) sulfate pastes according to the invention can also contain stabilizing additives such as e.g. Contain EDTA, NTA, phosphonates as complexing agents; to reduce viscosity, the addition of liquefying agents such as Alcohols, glycols, polyglycols and / or polyols possible.
  • stabilizing additives such as e.g. Contain EDTA, NTA, phosphonates as complexing agents; to reduce viscosity, the addition of liquefying agents such as Alcohols, glycols, polyglycols and / or polyols possible.
  • the magnesium (ether) sulfate pastes according to the invention can be used to produce surface-active preparations, such as washing, rinsing, cleaning and fabric softening detergents, and cosmetic and / or pharmaceutical preparations for the care and cleaning of skin, hair, mouth and teeth, such as hair lotions , Bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, stick preparations or ointments, preferably hair shampoos.
  • surface-active preparations such as washing, rinsing, cleaning and fabric softening detergents, and cosmetic and / or pharmaceutical preparations for the care and cleaning of skin, hair, mouth and teeth, such as hair lotions , Bubble baths, shower baths, creams, gels, lotions, alcoholic and aqueous / alcoholic solutions, emulsions, wax / fat masses, stick preparations or ointments, preferably hair shampoos.
  • agents can also be used as further auxiliaries and additives, mild surfactants, oil bodies, emulsifiers, superfatting agents, pearlescent waxes, consistency agents, thickeners, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, stabilizers, biogenic active ingredients, deodorants, antiperspirants, antidandruff agents, film formers, Contain swelling agents, UV light protection factors, antioxidants, hydrotropes, preservatives, insect repellents, self-tanners, tyrosine inhibitors (depigmentation agents), solubilizers, perfume oils, dyes and the like.
  • mild surfactants oil bodies, emulsifiers, superfatting agents, pearlescent waxes, consistency agents, thickeners, polymers, silicone compounds, fats, waxes, lecithins, phospholipids, stabilizers, biogenic active ingredients, deodorants, antiperspirants, antidandruff agents, film formers, Conta
  • Suitable mild, i.e. Particularly skin-compatible surfactants are fatty alcohol polyglycol ether sulfates, monoglyceride sulfates, mono- and / or dialkyl sulfosuccinates, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, fatty acid glutamates, ⁇ -olefin sulfonates, ether carboxylic acids,
  • Guerbet alcohols based on fatty alcohols with 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6-C22 fatty acids with linear C6-C22 fatty alcohols, esters of branched C6-C 3 carboxylic acids with linear C6 come as oil bodies, for example C22 fatty alcohols, for example myristyl myristate, myristyl palmitate, myristyl stearate, Myristylisostearat, myristyl, Myristylbehenat, My- ristylerucat, cetyl myristate, cetyl palmitate, cetyl stearate, Cetylisostearat, cetyl oleate, cetyl behenate, Cety- lerucat, Stearylmyristat, stearyl palmitate, stearyl stearate, Stearylisostearat, stearyl oleate, stearyl behenate , Stearyl
  • esters of linear C6-C22 fatty acids with branched alcohols in particular 2-ethylhexanol
  • esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols in particular dioctyl malates
  • esters of linear and / or branched fatty acids with polyhydric alcohols such as eg propylene glycol, dimer diol or trimer triol
  • polyhydric alcohols such as eg propylene glycol, dimer diol or trimer triol
  • Guerbet alcohols triglycerides based on C ⁇ -Cio fatty acids
  • esters of C6-C22 fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids especially benzoic acid, esters of C2-Ci2-dicarboxylic acids with linear or branched alcohols with 1
  • Finsolv® TN linear or branched, symmetrical or asymmetrical dialkyl ethers with 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons, such as such as squalane, squalene or dialkylcyclohexanes.
  • Suitable emulsifiers are nonionic surfactants from at least one of the following groups:
  • Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g.
  • cellulose / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;
  • adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out.
  • Ci2 / i8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations.
  • Alkyl and / or alkenyl oligoglycosides their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
  • the glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to about 8 are suitable.
  • the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
  • Suitable partial glycerides are hydroxystearic acid monoglyceride, stearic acid diglyceride hydroxy, isostearic acid, Isostearinklarediglycerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolklaremoglycerid, Ricinolklarediglycerid, Linolklaremonoglycerid, linoleic acid diglyceride, LinolenTalkremonoglycerid, Linolenchurediglycerid, Erucaklaklamonoglycerid, erucic acid diglyceride, rid Weinchuremonoglycerid, Weinklarediglycerid, Citronenklamonoglycerid, Citronendiglyce-, Malic acid monoglyceride, malic acid diglyceride and their technical mixtures, which may still contain minor amounts of triglyceride from the manufacturing process. Addition products of 1 to 30, preferably 5 to
  • polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearates (Lameform® TGI), polyglyceryl-4 isostearates (Isolan® Gl 34), polyglyceryl-3 oleates, diisostearoyl polyglyearylate-3 (Isolan® PDI), Polyglyceryl-3 Methylglucose Distearate (Tego Care® 450), Polyglyceryl-3 Beeswax (Cera Bellina®), Polyglyceryl-4 Caprate (Polyglycerol Caprate T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane® NL) , Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimerate Is
  • polystyrene resin examples include the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, taig fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to 30 mol of ethylene oxide.
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylm -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are surface-active compounds which, in addition to a C ⁇ / i ⁇ alkyl or acyl group, contain at least one free amino group and at least one -COOH or -S0 3 H group in the molecule and are capable of forming internal salts.
  • ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each with about 8 to 18 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Ci2 / i8-acylsarcosine.
  • cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • Substances such as, for example, lanolin and lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
  • Pearlescent waxes are: alkylene glycol esters, especially ethylene glycol distearate; Fatty acid alkanolamides, especially coconut fatty acid diethanolamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms
  • Suitable consistency agents are primarily fatty alcohols or hydroxyfatty alcohols with 12 to 22 and preferably 16 to 18 carbon atoms and also partial glycerides, fatty acids or hydroxyfatty acids. A combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates is preferred.
  • Suitable thickeners are, for example, Aerosil types (hydrophilic silicas), polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates , (eg Carbopole® from Goodrich or Synthalene® from Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylol propane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides Electrolytes such as table salt and ammonium chloride.
  • Aerosil types hydrophilic silicas
  • polysaccharides in particular
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF) Condensation products of polyglycols and amines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxypropyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amodimethicones, copolymers of adipic acid and dimethyaminohydroxypropyldiethylenetriamine (Cartaretine® / Sando
  • Anionic, zwitterionic, amphoteric and nonionic polymers include, for example, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobomylacrylate copolymers, methyl vinyl ether / maleic anhydride copolymers and their esters, non-crosslinked acrylamide acrylamide and polyethylenethacrylate acrylamide and non-crosslinked acrylamide / polyacrylamide acrylamide and non-crosslinked acrylamide and with polyesters, non-crosslinked acrylamide and polyammonyl acrylate, with non-crosslinked acrylamide acrylamide and polyamides Copolymers, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxyproyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyr
  • Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and / or alkyl-modified silicone compounds, which can be both liquid and resinous at room temperature.
  • Simethicones which are mixtures of dimethicones with an average chain length of 200 to 300 dimethylsiloxane units and hydrogenated silicates, are also suitable.
  • a detailed overview of suitable volatile silicones can also be found by Todd et al. in Cosm.Toil. 91, 27 (1976).
  • fats are glycerides
  • waxes include natural waxes such as candelilla wax, camauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, walnut, lanolin (wool wax), fur fat , Ceresin, ozokerite (earth wax), petrolatum, paraffin waxes, micro waxes; chemically modified waxes (hard waxes), such as montan ester waxes, Sasol waxes, hydrogenated jojoba waxes, and synthetic waxes, such as polyalkylene waxes and polyethylene glycol waxes.
  • natural waxes such as candelilla wax, camauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax, bees
  • lecithins In addition to fats, fat-like substances such as lecithins and phospholipids can also be used as additives.
  • lecithins as those glycerophospholipids which are formed from fatty acids, glycerol, phosphoric acid and choline by esterification.
  • Lecithins are therefore often referred to in the art as phosphatidylcholines (PC) and follow the general formula
  • R typically represents linear aliphatic hydrocarbon radicals with 15 to 17 carbon atoms and up to 4 cis double bonds.
  • lecithins are the cephalins, which are also referred to as phosphatidic acids and are derivatives of 1,2-diacyl-sn-glycerol-3-phosphoric acids.
  • phospholipids are usually understood to be mono- and preferably diesters of phosphoric acid with glycerol (glycerol phosphates), which are generally classed as fats.
  • sphingosines or sphingolipids are also suitable.
  • Metal salts of fatty acids such as e.g. Magnesium, aluminum and / or zinc stearate or ricinoleate are used.
  • Biogenic active substances are, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.
  • Cosmetic deodorants counteract, mask or eliminate body odors.
  • Body odors arise from the action of skin bacteria on apocrine sweat, whereby unpleasant smelling breakdown products are formed. Accordingly, deodorants contain active ingredients which act as germ-inhibiting agents, enzyme inhibitors, odor absorbers or odor maskers.
  • germ-inhibiting agents such as.
  • Esterase inhibitors are suitable as enzyme inhibitors. These are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG). The substances inhibit the Enzyme activity and thereby reduce odor.
  • trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG).
  • esterase inhibitors include sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesteric, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and their esters, such as, for example, glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, Monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester and zinc glycinate.
  • sterol sulfates or phosphates such as, for example, lanosterol, cholesterol, campesteric, stigmasterol and sitosterol sulfate or phosphate
  • dicarboxylic acids and their esters such as, for example, glutaric acid,
  • Suitable odor absorbers are substances that absorb odor-forming compounds and can retain them to a large extent. They lower the partial pressure of the individual components and thus also reduce their speed of propagation. It is important that perfumes must remain unaffected. Odor absorbers are not effective against bacteria. They contain, for example, a complex zinc salt of ricinoleic acid or special, largely odorless fragrances, which are known to the person skilled in the art as "fixators", such as, for example, the main component. B. extracts of labdanum or styrax or certain abietic acid derivatives. Fragrance agents or perfume oils act as odor maskers, which, in addition to their function as odor maskers, give the deodorants their respective fragrance.
  • Perfume oils are, for example, mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches as well as resins and balms. Animal raw materials, such as civet and castoreum, are also suitable. Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citroneliyoxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include the jonones and methylcedryl ketone
  • the alcohols anethole, citronol , Eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes and balsams.
  • fragrance oils of lower volatility which are mostly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labdanum oil and lavandin oil.
  • Antiperspirants reduce sweat formation by influencing the activity of the eccrine sweat glands and thus counteract armpit wetness and body odor.
  • Aqueous or anhydrous formulations of antiperspirants typically contain the following ingredients:
  • auxiliaries such as B. thickeners or complexing agents and / or
  • non-aqueous solvents such as As ethanol, propylene glycol and / or glycerin.
  • Salts of aluminum, zirconium or zinc are particularly suitable as astringent antiperspirant active ingredients.
  • suitable antiperspirant active ingredients are e.g. Aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complex compounds e.g. B. with propylene glycol-1, 2nd Aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds, for. B. with amino acids such as glycine.
  • customary oil-soluble and water-soluble auxiliaries can be present in smaller amounts in antiperspirants.
  • Such oil soluble aids can e.g. his:
  • water-soluble additives are e.g. Preservatives, water-soluble fragrances, pH adjusters, e.g. Buffer mixtures, water soluble thickeners, e.g. water-soluble natural or synthetic polymers such as e.g. Xanthan gum, hydroxyethyl cellulose, polyvinyl pyrrolidone or high molecular weight polyethylene oxides.
  • Octopirox® (1-hydroxy-4-methyl-6- (2,4,4-trimythylpentyl) -2- (1H) -pyridone-monoethanolamine salt
  • Baypival Pirocton Olamin
  • Ketoconazol® (4- Acetyl-1 - ⁇ - 4- [2- (2.4-dichlorophenyl) r-2- (1 H -imidazol-1-ylmethyl) -1, 3-dioxylan-c-4-ylmethoxyphenyl ⁇ piperazine, selenium disulfide, sulfur colloidal, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinole polyhexylate, sulfur tar distillates, salicylic acid (or in combination with hexachlorophene), undexylene acid monoethanolamide Sulfosuccinate Na salt, Lamepon® UD (protein undecylenic acid condensate, zinc pyrethione, aluminum pyrition and
  • Common film formers are, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinylpyrrolidone, vinylpyrrolidone-vinyl acetate copolymers, polymers of the acrylic acid series, quaternary cellulose derivatives, collagen, hyaluronic acid or its salts and similar compounds.
  • Montmorillonites, clay minerals, pemules and alkyl-modified carbopol types can serve as swelling agents for aqueous phases. Further suitable polymers or swelling agents can be found in the overview by R. Lochhead in Cosm.Toil. 108, 95 (1993).
  • UV light protection factors are understood to mean, for example, organic substances (light protection filters) which are liquid or crystalline at room temperature and which are able to absorb ultraviolet rays and absorb the energy absorbed in the form of longer-wave radiation, e.g. To give off heat again.
  • UVB filters can be oil-soluble or water-soluble. As oil-soluble substances e.g. to call:
  • 4-aminobenzoic acid derivatives preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate;
  • esters of cinnamic acid preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene);
  • esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone;
  • esters of benzalmalonic acid preferably di-2-ethylhexyl 4-methoxybenzmalonate
  • Triazine derivatives e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyioxy) -1, 3,5-triazine and octyl triazone as described in EP 0818450 A1 or dioctyl butamido triazone (Uvasorb ® HEB);
  • Possible water-soluble substances are: > 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts;
  • UV-A filters -4'-methoxydibenzoyl-methane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds, as described in DE 19712033 A1 (BASF).
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble light protection pigments namely finely dispersed metal oxides or salts
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm.
  • the pigments can also be surface treated, i.e. are hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctyisilanes or simethicones, are particularly suitable as hydrophobic coating agents. So-called micro- or nanopigments are preferably used in sunscreens. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the overview by P.Finkel in S ⁇ FW-Journal 122, 543 (1996).
  • secondary light stabilizers of the antioxidant type can also be used, which interrupt the photochemical reaction chain which is triggered when UV radiation penetrates the skin.
  • Typical examples are amino acids (e.g. glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g. urocanic acid) and their derivatives, peptides such as D, L-carnosine, D-carnosine, L-carnosine and their derivatives (e.g. anserine) , Carotenoids, carotenes (e.g.
  • ⁇ -carotene, ⁇ -carotene, lycopene and their derivatives, chlorogenic acid and their derivatives, lipoic acid and their derivatives (e.g. dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (e.g.
  • thioredoxin glutathione, cysteine, Cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) and their salts , Dilaurylthiodipropionat, Distearylthiodipro- pionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) as well as sulfoximine compounds (e.g.
  • buthioninsulfoximines homocysteine sulfoximine, Butioninsulfone, penta-, hexa-, heptathioninsulfoximine
  • very low tolerable dosages e.g. pmol bis ⁇ mol / kg
  • metal chelators e.g. ⁇ -hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin
  • ⁇ -hydroxy acids e.g. citric acid, lactic acid, malic acid
  • humic acid bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and its derivatives, unsaturated fatty acids and their derivatives (e.g.
  • Hydrotropes such as ethanol, isopropyl alcohol, or polyols can also be used to improve the flow behavior.
  • Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups.
  • the polyols can also contain further functional groups, in particular amino groups, or be modified with nitrogen. Typical examples are
  • Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1,000 daltons;
  • Methyl compounds such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
  • Sugar alcohols with 5 to 12 carbon atoms such as sorbitol or mannitol,
  • Dialcohol amines such as diethanolamine or 2-amino-1, 3-propanediol.
  • Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Ordinance.
  • N, N-diethyl-m-toluamide, 1, 2-pentanediol or ethyl butylacetylaminopropionate are suitable as insect repellents, and dihydroxyacetone is suitable as a self-tanning agent.
  • Arbutin, kojic acid, coumaric acid and ascorbic acid (vitamin C) can be used as tyrosine inhibitors, which prevent the formation of melanin and are used in depigmenting agents.
  • Perfume oils include mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl benzylatepylpropionate, allyl cyclohexyl propyl pionate.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, ⁇ -isomethyl ionone and methyl cedryl ketone the alcohols anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes and balsams.
  • fragrance oils of lower volatility which are mostly used as aroma components, are also suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
  • the dyes which can be used are those substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes” by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
  • the total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40,% by weight, based on the composition.
  • the agents can be produced by customary cold or hot processes; the phase inversion temperature method is preferably used.
  • the sulfonation product is neutralized by means of a slurry of magnesium oxide, in particular by means of a slurry of a combination of magnesium oxide and sodium hydroxide solution.
  • the magnesium oxide was placed in water or in an aqueous solution with sodium hydroxide solution (Examples 1 to 5) and stirred for an hour.
  • the crude sulfation product was collected in a 5 m 3 assembly container with anchor stirrer.
  • the majority of the excess magnesium oxide was dissolved at 45 ° C. using sulfuric acid (20%).
  • the resulting pH was (3%) 8.5.
  • 30 kg of lactic acid were added, which resulted in a pH (3%) of 3.5.
  • This was kept at 45 ° C. for a period of 12 hours to dissolve the remaining magnesium oxide.
  • the product was discontinued.
  • a solution of NaOH (10%) was added slowly and in portions to the container, so that the rotating anchor stirrer immediately stirred the amount of alkali into the paste. It was ensured by constant pH control that the alkalinity of the total batch never rose above pH (3%) 6.
  • the crude sulfation product was collected in a 5 m 3 assembly container with anchor stirrer and homogenizer (intensive stirrer). The majority of the excess magnesium oxide was dissolved at 45 ° C. using sulfuric acid (20%). The resulting pH was (3%) 8.5. Then 30 kg of lactic acid were added, which resulted in a pH (3%) of 3.5. This was kept at 45 ° C. for a period of 12 hours to dissolve the remaining magnesium oxide. After the magnesium oxide had completely dissolved, the product was discontinued. For this purpose, a solution of NaOH (10%) was added slowly and in portions to the container so that the homogenizer immediately stirred the amount of alkali into the paste.
  • the crude sulfation product was collected in a 5 m 3 assembly container with anchor stirrer; this container was additionally provided with a bypass, through which the paste from the lower area of the container via a homogenizer ("Supraton”) back up into the loading was pumped around.
  • the acid and base were then added to the pump head of the homogenizer, which thus made it possible to directly disperse the added solutions.
  • the resulting pH in the bypass behind the homogenizer was also measured.
  • the majority of the excess magnesium oxide was dissolved at 45 ° C. using sulfuric acid (20% strength); the resulting pH was pH (3%): 8.5.
  • 30 kg of lactic acid were added, which resulted in a pH (3%) of 3.5. This was kept at 45 ° C.
  • the magnesium ether sulfate pastes according to the invention show good emulsifying and foaming properties.
  • the following tables show examples of their use in cleaning agents and cosmetic preparations.

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

Abstract

L'invention concerne des pâtes d'(éther)sulfate de magnésium présentant une teneur en matières solides d'au moins 30 % en poids, que l'on obtient par sulfatation d'alcools gras et/ou d'éthoxylates d'alcools gras, (II) mélange du produit de sulfatation obtenu avec une suspension aqueuse avec une base de magnésium, (III) par neutralisation consécutive de la base de magnésium encore contenue dans la pâte obtenue, jusqu'à un pH de 2 à 5, cela par addition d'un acide, et (IV) enfin par ajustement à un pH inférieur à 7 avec des bases.
EP00989946A 1999-12-14 2000-12-05 Procede de production de pates d'(ether)sulfate de magnesium Withdrawn EP1237893A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1999160098 DE19960098A1 (de) 1999-12-14 1999-12-14 Magnesium(ether)sulfat-Pasten
DE19960098 1999-12-14
PCT/EP2000/012206 WO2001044252A1 (fr) 1999-12-14 2000-12-05 Procede de production de pates d'(ether)sulfate de magnesium

Publications (1)

Publication Number Publication Date
EP1237893A1 true EP1237893A1 (fr) 2002-09-11

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EP (1) EP1237893A1 (fr)
DE (1) DE19960098A1 (fr)
WO (1) WO2001044252A1 (fr)

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DE102008013606A1 (de) * 2008-03-11 2009-09-17 Clariant International Ltd. Verfahren zur Herstellung fester Erdalkalimetallsalze sekundärer Paraffinsulfonsäuren

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DE4446362A1 (de) * 1994-12-23 1996-06-27 Henkel Kgaa Verfahren zur Herstellung wäßriger Konzentrate von Fettalkoholethersulfat-Erdalkalisalzen

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See references of WO0144252A1 *

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WO2001044252A1 (fr) 2001-06-21

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