EP1161519A1 - Method for producing surfactant granulates - Google Patents

Method for producing surfactant granulates

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Publication number
EP1161519A1
EP1161519A1 EP00914104A EP00914104A EP1161519A1 EP 1161519 A1 EP1161519 A1 EP 1161519A1 EP 00914104 A EP00914104 A EP 00914104A EP 00914104 A EP00914104 A EP 00914104A EP 1161519 A1 EP1161519 A1 EP 1161519A1
Authority
EP
European Patent Office
Prior art keywords
weight
surfactant granules
sulfates
granules according
monoglyceride
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Withdrawn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
EP00914104A
Other languages
German (de)
French (fr)
Inventor
Josef Koester
Anke Eggers
Werner Seipel
Celia Kosboth
Hermann Hensen
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.)
Cognis IP Management 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 EP1161519A1 publication Critical patent/EP1161519A1/en
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216—Solid or semisolid forms
    • A61K8/022—Powders; Compacted Powders
    • A61K8/0225—Granulated powders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • 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
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • 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
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • 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
    • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • 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
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the invention relates to the use of special surfactant granules for the production of surface-active agents, preferably detergents and cleaning agents, soaps and oral and dental care agents.
  • Solid monoglyceride (ether) su! Fate (DE 19641275 C1) are known from the prior art, which are produced, for example, by drying and simultaneous granulation in the thin layer, in what is known as the “flash dryer”.
  • the surfactants produced in this way have inadequate solution properties in detergents and cleaning agents. Accordingly, the object of the present invention was to provide a solid form of supply of monoglyceride (ether) sulfates, which allows preparation with little water and is characterized by an improved dissolving power in washing, rinsing and cleaning agents.
  • the invention relates to surfactant granules, obtainable in that 20 to 60 preferably 40 to 50% by weight aqueous pastes containing monoglyceride (ether) sulfates are subjected to drying with simultaneous granulation in the fluidized bed.
  • Another object of the invention is the use of these surfactant granules for the production of surface-active agents, preferably oral and dental care agents.
  • Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
  • the usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)].
  • the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 A1 (Henkel)].
  • Overviews of the chemistry of the monoglyceride sulfates are, for example, by AK Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and FU Ahmed J.Am.Oil.Chem.Soc. 67, 8 (1990).
  • the monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (I) CH 2 0 (CH 2 CH 2 0) x-COR 1
  • R 1 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal.
  • monoglyceride (ether) sulfates are the reaction products monoglyceride of lauric acid, coconut fatty, palmitic acid, stearic acid monoglyceride, tallow fatty ⁇ lkla- and ethylene oxide adducts thereof with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts.
  • Monoglyceride sulfates of the formula (I) are preferably used in which R 1 CO is a linear acyl radical having 8 to 18, preferably 12 to 14 carbon atoms, x, y and z are 0 and X is sodium.
  • aqueous pastes are dried and granulated which contain, as further surfactants, fatty alcohol sulfates, sulfosuccinates, olefin sulfonates, alkyl and / or alkenyl oligoglycosides.
  • the monoglyceride (ether) sulfate granules can be present in a mixture with granules of fatty alcohol sulfates, sulfosuccinates, olefin sulfonates, alkyl and / or alkenyl oligoglycosides, such as, for example, monoglyceride (ether) sulfate, fatty alcohol sulfate, alkyl and / or alkenyl oligoglycosides.
  • Granules granules.
  • Fatty alcohol sulfates are to be understood as primary aliphatic alkyl sulfates of the formula (II)
  • R 2 is a linear or branched, saturated or unsaturated hydrocarbon radical having 12 to 14 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • Fatty alcohol sulfates are known anionic surfactants, which are preferably obtained by sulfating native fatty alcohols or synthetic oxo alcohols and subsequent neutralization can be obtained.
  • fatty alcohol sulfates are the sodium salts of sulfation products of lauryl alcohol, isotridecyl alcohol, myristyl 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 unsaturated monomer fraction in the fatty alcoholization of dimerization attack.
  • Fatty alcohols with 12 to 14 carbon atoms such as for example technical C12 / 14 coconut alcohol sulfates and in particular lauryl alcohol, are preferably used.
  • Sulfosuccinates which are also referred to as sulfosuccinic acid esters, are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. They follow formula (III)
  • R 3 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms
  • R 3 is R 4 or X
  • m and n independently of one another are 0 or numbers from 1 to 10
  • X is an alkali or alkaline earth metal, ammonium, Alkylammonium, alkanolammonium or glucammonium.
  • maleic acid but preferably maleic anhydride, which are esterified in the first step with optionally ethoxylated primary alcohols. At this point, the mono / diester ratio can be adjusted by varying the amount of alcohol and the temperature.
  • bisulfite is added, which is usually carried out in the solvent methanol.
  • Typical examples are sulfosuccinic acid monoesters and / or diesters in the form of their sodium salts which are derived from fatty alcohols having 8 to 18, preferably 8 to 10 or 12 to 14, carbon atoms; the fatty alcohols can be etherified with an average of 1 to 10 and preferably 1 to 5 moles of ethylene oxide and have both a conventional and preferably a narrowed homolog distribution.
  • Examples include di-n-octyl sulfosuccinate and monolauryl 3EO sulfosuccinate in the form of their sodium salts.
  • Alkyl and / or alkenyl oligoglycosides used are known nonionic surfactants which follow the formula (IV),
  • R 5 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G represents a sugar radical having 5 or 6 carbon atoms
  • p represents numbers from 1 to 10.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • the index number p in the general formula (IV) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 5 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 5 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
  • Typical examples are Lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above.
  • Alkyl oligoglucosides based on hardened C12 / 14 coconut alcohol with a DP of 1 to 3 are preferred.
  • the agents according to the invention contain, as a further constituent, olefin sulfonates which are usually obtained by addition of SO 3 to olefins of the formula (V) and subsequent hydrolysis and neutralization,
  • R 6 and R 7 independently of one another represent H or alkyl radicals having 1 to 20 carbon atoms, with the proviso that R 6 and R 7 together have at least 6 and preferably 10 to 16 carbon atoms.
  • olefin sulfonates can be used which result when R 6 or R 7 are hydrogen.
  • Typical examples of olefin sulfonates used are the sulfonation products which are obtained by treating SO 3 with 1-, 2-butene, 1-, 2-, 3-hexene, 1-, 2-, 3-, 4-octene, 1- , 2-, 3-, 4-, 5-decene, 1-, 2-, 3-, 4-, 5-, 6- dodecene, 1-, 2-, 3-, 4-, 5-, 6- , 7-tetradecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-hexadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7- , 8-, 9-octadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-octadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-eicosen and
  • hydrolysis and neutralization are carried out, after which the olefin sulfonate is present in the mixture as alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium, glucammonium, preferably sodium salt.
  • the hydrolyzed ⁇ -olefin sulfonation product ie the ⁇ -olefin sulfonates, is composed of approximately 60% by weight alkanesulfonates and approximately 40% by weight hydroxyalkanesulfonates; 80 to 85% by weight of mono- and 15 to 20% by weight of disulfonates.
  • aqueous alkyl sulfate pastes usually contain the unsulfonated components in amounts of 0.2 to 10, preferably 0.4 to 5 and in particular 0.6 to 0.8. % By weight - based on the active substance content
  • Aqueous technical monoglyceride (ether) sulfate pastes contain between 0.6 and 10% by weight unsulfated components and 10 to 50 preferably 15 to 45 and in particular 20-35% by weight technical coconut monoglyceride sulfate Sodium salt.
  • the remaining 100% by weight of the pastes is water, and salts 0.1 to 20, preferably 0.5 to 5% by weight, based on the active substance content.
  • a preferred possibility is to subject the aqueous surfactant pastes to so-called SKET granulation.
  • SKET granulation This is to be understood as granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed.
  • Aqueous pastes of anionic surfactants and the liquid precursors can be introduced into the fluidized bed simultaneously or in succession via one or more nozzles.
  • Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m.
  • the SKET granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s.
  • the granules are preferably discharged from the fluidized bed via a size classification of the granules.
  • the classification can take place, for example, by means of a sieving device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the inflowing air is usually composed of the heated or unheated classifier air and the heated bottom air.
  • the soil air temperature is between 80 and 400, preferably 90 and 350 ° C.
  • a starting mass, for example a SKET granulate from an earlier test batch, is advantageously introduced at the beginning of the SKET granulation.
  • the water evaporates from the anionic surfactant paste, producing dried to dried germs, which are coated with further amounts of anionic surfactant and the liquid precursor, granulated and again dried at the same time.
  • the dried granulate contains 1 to 2% by weight of residual water.
  • An advantage of the granules is that they are not sticky and have high bulk densities in the range from 300 to 1200 and preferably 500 to 800 g / l.
  • the surfactant granules produced according to the invention are used for the production of surface-active agents.
  • the surface-active agents can be detergents, rinsing agents, cleaning agents, fabric softening agents and cosmetic preparations for the care and cleaning of skin and hair. They are preferably used for the manufacture of soaps and oral and dental care products.
  • the surfactant granules according to the invention in amounts of 0.1 to 60, preferably 0.5 to 45 and in particular 0.6 to 20% by weight, based on the preparations and calculated as Solid - can be used in surface-active agents, preferably soaps and oral and dental care products.
  • 0.1 to 20 particularly preferably 0.5 to 15 and in particular 0.6 to 45% by weight of the surfactant granules - as described above - in soaps 0.1 to 20 and in particular 0.6 to 5% by weight.
  • -% of the surfactant granules used in oral and dental care products are particularly preferably 0.5 to 15 and in particular 0.6 to 45% by weight of the surfactant granules - as described above - in soaps 0.1 to 20 and in particular 0.6 to 5% by weight.
  • the use ratio of the surfactant granules according to the invention and the surfactant granules mentioned to one another can be 20:80 to 80:20, preferably 30:70 to 70:30 and in particular 40:60 to 60:40 parts by weight.
  • the washing, rinsing and cleaning agents can also contain other typical ingredients, such as, for example, anionic surfactants, nonionic surfactants, builders, bleaching agents, bleach activators, detergency boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repeliants, foam inhibitors, and inorganic salts Contain fragrances and dyes.
  • anionic surfactants such as, for example, anionic surfactants, nonionic surfactants, builders, bleaching agents, bleach activators, detergency boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repeliants, foam inhibitors, and inorganic salts Contain fragrances and dyes.
  • cosmetic preparations such as, for example, anionic surfactants, nonionic surfactants, builders, bleaching agents, bleach activators, detergency boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repeliants, foam inhibitors, and inorganic salt
  • the surfactant mixtures according to the invention can be used to produce cosmetic preparations, such as, for example, hair shampoos, hair lotions, foam baths, shower baths, creams, gels, lotions, emulsions, wax / fat compositions, stick preparations or powder.
  • These 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, stabilizers, biogenic agents, deodorant agents, antidandruff agents, film formers, swelling agents, UV agents. Contain sun protection factors, antioxidants, hydrotropes, preservatives, insect repellents, self-tanners, solubilizers, perfume oils, dyes, germ-inhibiting agents and the like.
  • the bar soaps can have water-soluble or water-swelling structurants as builders, such as starch, preferably wheat or corn starch.
  • builders can also contain finely divided, water-insoluble alkali aluminum silicates, the use of synthetic, bound water-containing crystalline sodium aluminosilicates and in this case particularly of zeolite A being particularly preferred; Zeolite NaX and its mixtures with zeolite NaA can also be used.
  • Suitable zeolites have a calcium binding capacity in the range from 100 to 200 mg CaO / g. NTA and / or EDTA can also be used as liquid builders.
  • Suitable plasticizers are fatty alcohols, fatty acid partial glycerides or wax esters, each with 12 to 22 carbon atoms in the fat residues.
  • the surfactant granules according to the invention can be used for the production of oral and dental care products.
  • the agents may also contain abrasives and polishes, aroma components, chitosans and other typical ingredients for toothpastes as further auxiliaries and additives.
  • the agents according to the invention can be chalk, dicalcium phosphate, sodium bicarbonate, sodium sulfate, insoluble sodium metaphosphate, aluminum silicate, layer silicates, hydrotalcites, calcium pyrophosphate, fine-particle synthetic resins, silicas, aluminum oxide, aluminum oxide trihydrate, talc, zeolites, calcium aluminum sulfate, magnesium aluminum sulfate and / or contain magnesium oxide.
  • the share of grinding and Polishing agent can be 1 to 25, preferably 10 to 20% by weight, based on the finished preparations.
  • auxiliary substances and additives are also flavor components, for example peppermint oil, spearmint oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel, cinnamon oil, clove oil, geranium oil, sage oil, allspice oil, thyme oil, marjoram oil, basil oil, citrus oil or one or more components of these oils isolated or synthetically produced, such as Menthol, carvone, anethole, cineol, eugenol, cinnamaldehyde, cargophylls, geraniol, citronellol, linalool, salves, thymol, terpinan, terpinol, methylchavicol and methyl salicylate.
  • Suitable flavors are e.g. Methyl acetate, vanillin, lonone, linalyl acetate, rhodinol and piperiton.
  • Either natural sugars such as sucrose, maltose, lactose and fructose or synthetic sweeteners such as e.g. Saccharin sodium salt, sodium cyclamate or aspartame.
  • the proportion of the flavoring substances can be 0 to 3, preferably 1 to 2% by weight, based on the finished preparations.
  • Chitosans are biopolymers and belong to the group of hydrocolloids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit:
  • chitosans are cationic biopolymers under these conditions.
  • the positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products and pharmaceuticals Preparations used (cf. Ullmann 's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pp. 231-332).
  • Overviews on this topic have also been published, for example, by B. Gesslein et al. in HAPPI 27, 57 (1990), O.Skaugrud in Drug Cosm. Ind. 148: 24 (1991) and E. Onoyen et al.
  • chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials.
  • the chitin is used in a process that was first developed by Hackmann et al. has been described Usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, the molecular weights being able to be distributed over a broad spectrum.
  • Appropriate methods are, for example, made from Makromol. Chem. 177, 3589 (1976) or French patent application FR 2701266 A.
  • German patent applications DE 4442987 A1 and DE 19537001 A1 (Henkel), which have an average molecular weight of 800,000 to 1,200,000 Daltons, a Brookfield viscosity (1% by weight in Glycolic acid) below 5000 mPas, a degree of deacetylation in the range from 80 to 88% and an ash content of less than 0.3% by weight.
  • chitosans as typical cationic biopolymers
  • anionically or nonionically derivatized chitosans such as, for example, carboxylation, succinylation or alkoxylation products, as described, for example, in German patent DE 3713099 C2 (L'Oreal) and in German, are also suitable for the purposes of the invention
  • Patent application DE 19604180 A1 (Henkel) can be described.
  • the proportion of chitosans can be 0 to 2, preferably 0.1 to 0.5% by weight, based on the finished preparations.
  • humectants such as e.g. Sorbitol, glycerin or polyethylene glycols, consistency regulators, deodorising agents, swelling agents and binders, such as e.g. Carboxymethyl cellulose or xanthan gum, active substances against mouth and tooth diseases, water-soluble fluorine compounds such as Sodium fluoride or sodium monofluorophosphate.
  • auxiliaries and additives overall is not critical per se and depends on the type of agent that is ultimately to be assembled.
  • the proportion will usually be 5 to 98% by weight and preferably 80 to 90% by weight, based on the finished preparations.
  • a typical toothpaste has the following typical composition (water ad 100% by weight):
  • Example 1 an acidic sulfuric acid half-ester of coconut monoglyceride (KMGSS) was spray-neutralized using a multi-component nozzle with 50% by weight sodium hydroxide solution (propellant gas: ammonia) and directly in a plant for granulation drying (AGT) according to the teaching of EP 0319819 A1 Glatt (Germany) dried and granulated at the same time.
  • AGT granulation drying
  • a surfactant granulate was used as starting mass, which had been produced in a previous batch (under the same process conditions) and had approximately the same composition as the finished granules of Examples 1 and 2.
  • the process conditions can be found in Table 1.
  • the surfactant mixtures were used in a standard toothpaste formulation.
  • the foaming power was determined according to the friction foam method in an EHMEDA friction foam device [greases, soaps, paints. 66, 955 (1964)].
  • 20 g of toothpaste were dispersed in 180 g of water and heated to 45 ° C. in the foam cylinder.
  • 60 seconds of friction with a vertically rotating Perlon brush at 2600 rpm generated foam on a cylindrically shaped metal wire mesh.
  • Examples 1 to 3 in Table 1 are according to the invention, Examples V1 to V3 serve for comparison.

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Abstract

The invention relates to surfactant granulates which are obtained by subjecting mono-glyceride (ether) sulfates which contain 20 to 60 percent by weight aqueous paste to drying and simultaneous granulation in a fluidised bed.

Description

VERFAHREN ZUR HERSTELLUNG VON TENSIDGRANULATENMETHOD FOR PRODUCING TENSIDE GRANULES
Gebiet der ErfindungField of the Invention
Die Erfindung betrifft den Einsatz von speziellen Tensidgranulaten zur Herstellung von oberflächenaktiven Mitteln, vorzugsweise Wasch- und Reinigungsmitteln, Seifen und Mund- und Zahnpflegemitteln.The invention relates to the use of special surfactant granules for the production of surface-active agents, preferably detergents and cleaning agents, soaps and oral and dental care agents.
Stand der TechnikState of the art
Monoglycerid(ether)sulfate gewinnen aufgrund ihrer ausgezeichneten Detergenseigenschaften zunehmend an Bedeutung für die Verwendung in oberflächenaktiven Mitteln. Sie werden bislang in der Regel als wäßrige Zubereitungen eingesetzt. Von großem Nachteil ist hierbei, daß diese Pasten in der Regel zwischen 50 und 75 Gew.-% Wasser enthalten, um hinreichend pumpbar zu sein. Im Markt besteht jedoch ein starkes Bedürfnis an festen, wasserfreien Anbietungsformen, die sich ohne vorherige Trocknung insbesondere in Pulverwaschmittel, Zahncremes oder Syndetseifen einarbeiten lassen.Because of their excellent detergent properties, monoglyceride (ether) sulfates are becoming increasingly important for use in surface-active agents. So far, they have generally been used as aqueous preparations. A great disadvantage here is that these pastes generally contain between 50 and 75% by weight of water in order to be sufficiently pumpable. However, there is a strong demand on the market for solid, water-free forms of supply which can be incorporated without prior drying, in particular in powder detergents, toothpastes or syndet soaps.
Aus dem Stand der Technik sind feste Monoglycerid(ether)su!fate (DE 19641275 C1) bekannt, welche beispielsweise durch Trocknung und gleichzeitige Granulierung in der Dünnschicht, im sogenannten "Flash dryer", erzeugt werden. Die auf diese Weise hergestellten Tenside weisen jedoch in Wasch- und Reinigungsmitteln unzureichende Lösungseigenschaften auf. Demzufolge hat die Aufgabe der vorliegenden Erfindung darin bestanden, eine feste Anbietungsform von Monoglycerid(ether)sulfaten zur Verfügung zu stellen, die eine Zubereitung mit wenig Wasser erlaubt und sich durch ein verbessertes Auflösungsvermögen in Wasch-, Spül- und Reinigungsmitteln auszeichnet.Solid monoglyceride (ether) su! Fate (DE 19641275 C1) are known from the prior art, which are produced, for example, by drying and simultaneous granulation in the thin layer, in what is known as the “flash dryer”. However, the surfactants produced in this way have inadequate solution properties in detergents and cleaning agents. Accordingly, the object of the present invention was to provide a solid form of supply of monoglyceride (ether) sulfates, which allows preparation with little water and is characterized by an improved dissolving power in washing, rinsing and cleaning agents.
Beschreibung der ErfindungDescription of the invention
Gegenstand der Erfindung sind Tensidgranulate, dadurch erhältlich, daß man 20 bis 60 vorzugsweise 40 bis 50 Gew.-%ige wäßrige Pasten enthaltend Monoglycerid(ether)sulfate einer Trocknung unter gleichzeitiger Granulierung in der Wirbelschicht unterwirft. Ein weiterer Gegenstände der Erfindung ist die Verwendung dieser Tensidgranulate zur Herstellung von oberflächenaktiven Mitteln, vorzugsweise Mund- und Zahnpflegemittel. Überraschenderweise wurde gefunden, daß die Trocknung und Granulierung wäßriger Tensidpasten in der Wirbelschicht (,,Sket"-Granulierung) zu festen Dareichungsformen des Monog lycerid (ether)sulfats führt, die sich durch ausgezeichnetes Auflösevermögen in Wasch- Spül-, und Reinigungsmitteln auszeichnen. Darüber hinaus zeigen auf diese Weise hergestellte Monoglycerid(ether)sulfat-Granulate in Mund- und Zahnpflegemittel eine abrasive Wirkung und können somit als Ersatz für andere Abrasivstoffe dienen. Besonders vorteilhaft ist, daß hierdurch die Einsatzmenge an Putzkörpern verringert werden kann, ohne dabei die Putzleistung zu verschlechtern. Stückseifen, welche Monoglycerid(ether)sulfat-Granulate als Tensidkomponente enthalten, zeichnen sich durch ein gutes Schaumvermögen, eine bessere Stabilität an der Luft und einer verminderte Versumpfungsneigung aus.The invention relates to surfactant granules, obtainable in that 20 to 60 preferably 40 to 50% by weight aqueous pastes containing monoglyceride (ether) sulfates are subjected to drying with simultaneous granulation in the fluidized bed. Another object of the invention is the use of these surfactant granules for the production of surface-active agents, preferably oral and dental care agents. Surprisingly, it was found that the drying and granulation of aqueous surfactant pastes in the fluidized bed ("sket" granulation) leads to solid dosage forms of monoglyceride (ether) sulfate which are distinguished by excellent dissolving power in washing-up, washing-up and cleaning agents In addition, monoglyceride (ether) sulfate granules produced in this way have an abrasive effect in oral and dental care products and can therefore serve as a substitute for other abrasives, and it is particularly advantageous that the amount of cleaning agents used can be reduced without reducing the cleaning performance Bar soaps which contain monoglyceride (ether) sulfate granules as the surfactant component are notable for good foaming power, better stability in the air and a reduced tendency to sump.
In Abmischung mit anderen Tensiden, insbesondere Fettalkoholsulfate, Sulfosuccinate, Olefinsulfonate, Alkyl- und/oder Alkenyloligoglykoside wird eine synergistische Verstärkung der genannten Eigenschaften beobachtet. Darüber hinaus ist die Entfernung von Wasser, welche beim Einsatz vergleichbarer wäßriger Pasten erforderlich wäre, bei der Verwendung dieser Granulate in den beschriebenen Mitteln überflüssig.When mixed with other surfactants, in particular fatty alcohol sulfates, sulfosuccinates, olefin sulfonates, alkyl and / or alkenyl oligoglycosides, a synergistic enhancement of the properties mentioned is observed. In addition, the removal of water, which would be required when using comparable aqueous pastes, is unnecessary when using these granules in the agents described.
Monoglycerid(ether)sulfatMonoglyceride (ether) sulfate
Monoglyceridsulfate und Monoglyceridethersulfate stellen bekannte anionische Tenside dar, die nach den einschlägigen Methoden der präparativen organischen Chemie erhalten werden können. Üblicherweise geht man zu ihrer Herstellung von Triglyceriden aus, die gegebenenfalls nach Ethoxylierung zu den Monoglyceriden umgeestert und nachfolgend sulfatiert und neutralisiert werden. Gleichfalls ist es möglich, die Partialglyceride mit geeigneten Sulfatierungsmitteln, vorzugsweise gasförmiges Schwefeltrioxid oder Chlorsulfonsäure umzusetzen [vgl. EP 0561825 B1, EP 0561999 B1 (Henkel)]. Die neutralisierten Stoffe können - falls gewünscht - einer Ultrafiltration unterworfen werden, um den Elektrolytgehalt auf ein gewünschtes Maß zu vermindern [DE 4204700 A1 (Henkel)]. Übersichten zur Chemie der Monoglyceridsulfate sind beispielsweise von A. K. Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) und F. U. Ahmed J.Am.Oil.Chem.Soc. 67, 8 (1990) erschienen. Die im Sinne der Erfindung einzusetzenden Monoglycerid(ether)sulfate folgen der Formel (I) CH20(CH2CH20)x-COR1 Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. The usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)]. If desired, the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 A1 (Henkel)]. Overviews of the chemistry of the monoglyceride sulfates are, for example, by AK Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) and FU Ahmed J.Am.Oil.Chem.Soc. 67, 8 (1990). The monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (I) CH 2 0 (CH 2 CH 2 0) x-COR 1
I CH-0(CH2CH20)yHI CH-0 (CH 2 CH 2 0) y H
(I)(I)
in der R1CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Mono- glycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäu- remonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vor-zugsweise werden Monoglyceridsulfate der Formel (I) eingesetzt, in der R1CO für einen linearen Acylrest mit 8 bis 18, vorzugsweise 12 bis 14 Kohlenstoffatomen, x, y und z für 0 und X für Natrium steht.in which R 1 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30, preferably 2 to 10, and X stands for an alkali or alkaline earth metal. Typical examples of suitable within the meaning of the invention, monoglyceride (ether) sulfates are the reaction products monoglyceride of lauric acid, coconut fatty, palmitic acid, stearic acid monoglyceride, tallow fatty Ölsäu- and ethylene oxide adducts thereof with sulfur trioxide or chlorosulfonic acid in the form of their sodium salts. Monoglyceride sulfates of the formula (I) are preferably used in which R 1 CO is a linear acyl radical having 8 to 18, preferably 12 to 14 carbon atoms, x, y and z are 0 and X is sodium.
Tenside / TensidgranulateSurfactants / surfactant granules
In einer bevorzugten Ausführungsform der Erfindung werden wäßrige Pasten getrocknet und granuliert, die als weitere Tenside Fettalkoholsulfate, Sulfosuccinate, Olefinsulfonate, Alkyl- und/oder Alkenyloligoglykoside enthalten. Alternativ können die Monoglycerid(ether)sulfatgranu- late in Mischung mit Granulaten von Fettalkoholsulfaten, Sulfosucci-naten, Olefinsulfonaten, Alkyl- und/oder Alkenyloligoglykosiden vorliegen, wie beispielsweise Monoglycerid(ether)sulfat-, Fettalkoholsulfat-, Alkyl- und/oder Alkenyloligoglykosid-Granulate.In a preferred embodiment of the invention, aqueous pastes are dried and granulated which contain, as further surfactants, fatty alcohol sulfates, sulfosuccinates, olefin sulfonates, alkyl and / or alkenyl oligoglycosides. Alternatively, the monoglyceride (ether) sulfate granules can be present in a mixture with granules of fatty alcohol sulfates, sulfosuccinates, olefin sulfonates, alkyl and / or alkenyl oligoglycosides, such as, for example, monoglyceride (ether) sulfate, fatty alcohol sulfate, alkyl and / or alkenyl oligoglycosides. Granules.
FettalkoholsulfateFatty alcohol sulfates
Unter Fettalkoholsulfaten sind primäre aliphatische Alkylsulfate der Formel (II) zu verstehen,Fatty alcohol sulfates are to be understood as primary aliphatic alkyl sulfates of the formula (II)
R 0-S03X (II)R 0-S0 3 X (II)
in der R2für einen linearen oder verzweigten, gesättigten oder ungesättigten Kohlenwasserstoffrest mit 12 bis 14 Kohlenstoffatomen und X für ein Alkali- und/oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Fettalkoholsulfate stellen bekannte anionische Tenside dar, die vorzugsweise durch Sulfatierung von nativen Fettalkoholen oder synthetischen Oxoalkoholen und nachfolgende Neutralisation erhalten werden. Typische Beispiele für Fettalkoholsulfate stellen die Natriumsalze von Sulfatierungsprodukten des Laurylalkohols, Isotridecylalkohols, Myristylalkohols, sowie deren technische Mischungen, die z.B. bei der Hochdruckhydrierung von technischen Methylestern auf Basis von Fetten und Ölen oder Aldehyden aus der Roelenschen Oxosynthese sowie als Monomerfraktion bei der Dimerisierung von ungesättigten Fettalkoholen anfallen. Vorzugsweise werden Fettalkohole mit 12 bis 14 Kohlenstoffatomen, wie beispielsweise technische C12/14 Kokosalkoholsulfate und insbesondere Laurylalkohol verwendet.in which R 2 is a linear or branched, saturated or unsaturated hydrocarbon radical having 12 to 14 carbon atoms and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium. Fatty alcohol sulfates are known anionic surfactants, which are preferably obtained by sulfating native fatty alcohols or synthetic oxo alcohols and subsequent neutralization can be obtained. Typical examples of fatty alcohol sulfates are the sodium salts of sulfation products of lauryl alcohol, isotridecyl alcohol, myristyl 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 unsaturated monomer fraction in the fatty alcoholization of dimerization attack. Fatty alcohols with 12 to 14 carbon atoms, such as for example technical C12 / 14 coconut alcohol sulfates and in particular lauryl alcohol, are preferably used.
SulfosuccinateSulfosuccinates
Sulfosuccinate, die auch als Sulfobemsteinsäureester bezeichnet werden, stellen bekannte anionische Tenside dar, die nach den einschlägigen Methoden der präparativen organischen Chemie erhalten werden können. Sie folgen der Formel (III),Sulfosuccinates, which are also referred to as sulfosuccinic acid esters, are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. They follow formula (III)
SO3XSO3X
II.
R3(OCH2CH2)nOOC-CH-CH2-COO(CH2CH2θ)mR4 (III)R3 (OCH2CH 2 ) nOOC-CH-CH 2 -COO (CH2CH2θ) mR 4 (III)
in der R3 für einen Alkyl- und/oder Alkenylrest mit 6 bis 22 Kohlenstoffatomen, R3 für R4 oder X, m und n unabhängig voneinander für 0 oder Zahlen von 1 bis 10 und X für ein Alkali- oder Erdalkalimetall, Ammonium, Alkylammonium, Alkanolammonium oder Glucammonium steht. Zu ihrer Herstellung geht man üblicherweise von Maleinsäure, vorzugsweise aber Maleinsäureanhydrid aus, die im ersten Schritt mit gegebenenfalls ethoxylierten primären Alkoholen verestert werden. An dieser Stelle kann durch Variation von Alkoholmenge und Temperatur das Mono-/Diester-Verhältnis eingestellt werden. Im zweiten Schritt erfolgt die Anlagerung von Bisulfit, die üblicherweise im Lösungsmittel Methanol durchgeführt wird. Neuere Übersichten zu Herstellung und Verwendung von Sulfosuccinaten sind beispielsweise von T. Schoenberg in Cosm.Toil. 104, 105 (1989), J. A. Milne in R.Soc.Chem. (Ind. Appl. Surf.II) 77, 77 (1990) sowie W. Hreczuch et al. in J.Am.Oil.Chem.Soc. 70, 707 (1993) erschienen. Typische Beispiele sind Sulfobernsteinsäuremono- und/oder -diester in Form ihrer Natriumsalze, die sich von Fettalkoholen mit 8 bis 18, vorzugsweise 8 bis 10 bzw. 12 bis 14 Kohlenstoffatomen ableiten; die Fettalkohole können dabei mit durchschnittlich 1 bis 10 und vorzugsweise 1 bis 5 Mol Ethylenoxid verethert sein und dabei sowohl eine konventionelle als auch vorzugsweise eine eingeengte Homologenverteilung aufweisen. Exemplarisch genannt seien Di-n-octylsulfosuccinat und Monolauryl-3EO-sulfosuccinat in Form ihrer Natriumsalze. Alkyl- und/oder Alkenyloliqoqlykosidein which R 3 is an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, R 3 is R 4 or X, m and n independently of one another are 0 or numbers from 1 to 10 and X is an alkali or alkaline earth metal, ammonium, Alkylammonium, alkanolammonium or glucammonium. For their preparation, one usually starts from maleic acid, but preferably maleic anhydride, which are esterified in the first step with optionally ethoxylated primary alcohols. At this point, the mono / diester ratio can be adjusted by varying the amount of alcohol and the temperature. In the second step, bisulfite is added, which is usually carried out in the solvent methanol. Recent reviews on the production and use of sulfosuccinates are, for example, from T. Schoenberg in Cosm.Toil. 104, 105 (1989), JA Milne in R.Soc.Chem. (Ind. Appl. Surf.II) 77, 77 (1990) and W. Hreczuch et al. in J.Am.Oil.Chem.Soc. 70, 707 (1993). Typical examples are sulfosuccinic acid monoesters and / or diesters in the form of their sodium salts which are derived from fatty alcohols having 8 to 18, preferably 8 to 10 or 12 to 14, carbon atoms; the fatty alcohols can be etherified with an average of 1 to 10 and preferably 1 to 5 moles of ethylene oxide and have both a conventional and preferably a narrowed homolog distribution. Examples include di-n-octyl sulfosuccinate and monolauryl 3EO sulfosuccinate in the form of their sodium salts. Alkyl and / or alkenyl olefin glycosides
Alkyl- und/oder Alkenyloligoglykosiden eingesetzt stellen bekannte nichtionische Tenside dar, die der Formel (IV) folgen,Alkyl and / or alkenyl oligoglycosides used are known nonionic surfactants which follow the formula (IV),
(IV)(IV)
in der R5 für einen Alkyl- und/oder Alkenylrest mit 4 bis 22 Kohlenstoffatomen, G für einen Zuckerrest mit 5 oder 6 Kohlenstoffatomen und p für Zahlen von 1 bis 10 steht. Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden. Stellvertretend für das umfangreiche Schrifttum sei hier auf die Übersichtsarbeit von Biermann et al. in Starch/Stärke 45, 281 (1993), B. Salka in Cosm.Toil. 108, 89 (1993) sowie J. Kahre et al. in SÖFW-Journal Heft 8, 598 (1995) verwiesen.in which R 5 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. Representative of the extensive literature here is the review by Biermann et al. in Starch /force 45, 281 (1993), B. Salka in Cosm.Toil. 108, 89 (1993) and J. Kahre et al. in SÖFW-Journal Issue 8, 598 (1995).
Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkyl- und/oder Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der allgemeinen Formel (IV) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung stets ganzzahlig sein muß und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren Oligomerisierungsgrad p von 1 ,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1 ,7 ist und insbesondere zwischen 1 ,2 und 1 ,4 liegt. Der Alkyl- bzw. Alkenylrest R5 kann sich von primären Alkoholen mit 4 bis 11 , vorzugsweise 8 bis 10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der Roelenschen Oxosynthese erhalten werden. Bevorzugt sind Alkyloli- goglucoside der Kettenlänge Cs-Cio (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem Cβ-Cis-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% Ci2-Alkohol verunreinigt sein können sowie Alkyloligoglucoside auf Basis technischer Cg/n-Oxo- alkohole (DP = 1 bis 3). Der Alkyl- bzw. Alkenylrest R5 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise 12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside auf Basis von gehärtetem C12/14- Kokosalkohol mit einem DP von 1 bis 3.The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (IV) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R 5 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length Cs-Cio (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical Cβ-Cis coconut fatty alcohol by distillation and are contaminated with a proportion of less than 6% by weight of Ci2-alcohol can as well as alkyl oligoglucosides based on technical Cg / n oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R 5 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are Lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C12 / 14 coconut alcohol with a DP of 1 to 3 are preferred.
OlefinsulfonateOlefin sulfonates
Die erfindungsgemäßen Mittel enthalten als weiteren Bestandteil Olefinsulfonate, die man üblicherweise durch Anlagerung von S03 an Olefine der Formel (V) und nachfolgender Hydrolyse und Neutralisation erhält,The agents according to the invention contain, as a further constituent, olefin sulfonates which are usually obtained by addition of SO 3 to olefins of the formula (V) and subsequent hydrolysis and neutralization,
wobei R6 und R7 unabhängig voneinander für H oder Alkylreste mit 1 bis 20 Kohlenstoffatomen stehen, mit der Maßgabe, daß R6 und R7 zusammen mindestens 6 und vorzugsweise 10 bis 16 Kohlenstoffatome aufweisen. Hinsichtlich Herstellung und Verwendung sei auf den Übersichtsartikel J.Am.Oil. Chem.Soc. 55, 70 (1978) verwiesen.wherein R 6 and R 7 independently of one another represent H or alkyl radicals having 1 to 20 carbon atoms, with the proviso that R 6 and R 7 together have at least 6 and preferably 10 to 16 carbon atoms. Regarding production and use, see the review article J.Am.Oil. Chem.Soc. 55, 70 (1978).
Es können innerständige Olefinsulfonate, aber vorzugsweise α-Olefinsulfonate eingesetzt werden, die sich ergeben wenn R6 oder R7 für Wasserstoff stehen. Typische Beispiele für genutzte Olefinsulfonate sind die Sulfonierungsprodukte, die man erhält, indem man S03 mit 1-, 2-Buten, 1-, 2-, 3-Hexen, 1-, 2-, 3-, 4-Octen, 1-, 2-, 3-, 4-, 5-Decen, 1-, 2-, 3-, 4-, 5-, 6- Dodecen, 1-, 2-, 3-, 4-, 5-, 6-, 7-Tetradecen, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-Hexadecen, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-Octadecen, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-Eicosen und 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- und 11- Docosen umsetzt. Nach erfolgter Sulfonierung wird eine Hydrolyse und Neutralisation durchgeführt, wonach das Olefinsulfonat als Alkali-, Erdalkali-, Ammonium-, Alkylammonium-, Alkanolammonium-, Glucammonium-, vorzugsweise Natrium-Salz in der Mischung vorliegt. Das hydrolysierte α- Olefinsulfonierungsprodukt, die α-Olefinsulfonate also, setzen sich aus ca. 60 Gew.-% Alkansulfonate und ca. 40 Gew.-% Hydroxyalkansulfonate zusammen; hiervon sind 80 bis 85 Gew.-% Mono- und 15 bis 20 Gew.-% Disulfonate.Internal olefin sulfonates, but preferably α-olefin sulfonates, can be used which result when R 6 or R 7 are hydrogen. Typical examples of olefin sulfonates used are the sulfonation products which are obtained by treating SO 3 with 1-, 2-butene, 1-, 2-, 3-hexene, 1-, 2-, 3-, 4-octene, 1- , 2-, 3-, 4-, 5-decene, 1-, 2-, 3-, 4-, 5-, 6- dodecene, 1-, 2-, 3-, 4-, 5-, 6- , 7-tetradecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-hexadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7- , 8-, 9-octadecene, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-eicosen and 1-, 2-, 3-, 4- , 5-, 6-, 7-, 8-, 9-, 10- and 11-docosen. After sulfonation has been carried out, hydrolysis and neutralization are carried out, after which the olefin sulfonate is present in the mixture as alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium, glucammonium, preferably sodium salt. The hydrolyzed α-olefin sulfonation product, ie the α-olefin sulfonates, is composed of approximately 60% by weight alkanesulfonates and approximately 40% by weight hydroxyalkanesulfonates; 80 to 85% by weight of mono- and 15 to 20% by weight of disulfonates.
Trocknen und GranulierenDrying and granulating
Neben der Trocknung und Granulierung neutralisierter Tensidpasten ist es ferner ebenso möglich, die sauren Sulfierungsprodukte einer Sprühneutralisation zu unterwerfen, wie sie beispielsweise in der EP 0319819 A1 beschrieben wird. Dabei werden die Säure und eine hochkonzentrierte wäßrige Natronlauge getrennt mit einem gasförmigen Medium beaufschlagt, anschließend in stöchiometrischen Mengen zusammengeführt, in einer Mehrstoffdüse neutralisiert und bei einem hohen Treibgasdruck in die Trocknungs- bzw. Granulierungsanlagen versprüht. Da die Sulfatierung, vor allem in großtechnischen Anlagen, nicht vollständig verläuft enthalten die herkömmlichen Alkylsulfat-Pasten auch stets sogenannte unsulfierte Anteile. Unter diesen unsulfierten Anteilen werden bei Monoglyceridsulfaten die nicht umgesetzten Monoglyceride verstanden. Üblicher-weise enthalten die wäßrigen Alkylsulfat-Pasten die unsulfierten Anteile in Mengen von 0,2 bis 10 vorzugsweise 0,4 bis 5 und insbesondere 0,6 bis 0,8. Gew.-%- bezogen auf den Aktivsubstanzgehalt Wäßrige technische Monoglycerid(ether)sulfat-Pasten erhalten zwischen 0,6 und 10 Gew.-% unsulfierte Anteile sowie 10 bis 50 vorzugsweise 15 bis 45 und insbesondere 20-35 Gew.-% technisches Kokosmonoglyceridsulfat-Natriumsalz. Der zu 100 Gew.- % fehlende Rest der Pasten ist Wasser, und Salze 0,1 bis 20, vorzugsweise 0,5 bis 5 Gew.-%- bezogen auf den Aktivsubstanzgehalt-.In addition to drying and granulating neutralized surfactant pastes, it is also possible to spray neutralize the acidic sulfation products, as described for example in EP 0319819 A1 is described. The acid and a highly concentrated aqueous sodium hydroxide solution are separately charged with a gaseous medium, then combined in stoichiometric amounts, neutralized in a multi-component nozzle and sprayed into the drying or granulating plants at a high propellant gas pressure. Since the sulfation, especially in large-scale plants, does not proceed completely, the conventional alkyl sulfate pastes always contain so-called unsulfated components. In the case of monoglyceride sulfates, these unsulfonated fractions mean the unreacted monoglycerides. The aqueous alkyl sulfate pastes usually contain the unsulfonated components in amounts of 0.2 to 10, preferably 0.4 to 5 and in particular 0.6 to 0.8. % By weight - based on the active substance content Aqueous technical monoglyceride (ether) sulfate pastes contain between 0.6 and 10% by weight unsulfated components and 10 to 50 preferably 15 to 45 and in particular 20-35% by weight technical coconut monoglyceride sulfate Sodium salt. The remaining 100% by weight of the pastes is water, and salts 0.1 to 20, preferably 0.5 to 5% by weight, based on the active substance content.
SKET-GranulierunqSKET pelletizing
Eine bevorzugte Möglichkeit besteht darin, die wäßrigen Tensidpasten einer sogenannten SKET- Granulierung zu unterwerfen. Hierunter ist eine Granulierung unter gleichzeitiger Trocknung zu verstehen, die vorzugsweise batchweise oder kontinuierlich in der Wirbelschicht erfolgt. Dabei können wäßrige Pasten anionischer Tenside und die flüssigen Vorprodukte gleichzeitig oder nacheinander über eine oder mehrere Düsen in die Wirbelschicht eingebracht werden. Bevorzugt eingesetzte Wirbelschicht-Apparate besitzen Bodenplatten mit Abmessungen von 0,4 bis 5 m. Vorzugsweise wird die SKET-Granulierung bei Wirbelluftgeschwindigkeiten im Bereich von 1 bis 8 m/s durchgeführt. Der Austrag der Granulate aus der Wirbelschicht erfolgt vorzugsweise über eine Größenklassierung der Granulate. Die Klassierung kann beispielsweise mittels einer Siebvorrichtung oder durch einen entgegengeführten Luftstrom (Sichterluft) erfolgen, der so reguliert wird, daß erst Teilchen ab einer bestimmten Teilchengröße aus der Wirbelschicht entfernt und kleinere Teilchen in der Wirbelschicht zurückgehalten werden. Üblicherweise setzt sich die einströmende Luft aus der beheizten oder unbeheizten Sichterluft und der beheizten Bodenluft zusammen. Die Bodenlufttemperatur liegt dabei zwischen 80 und 400, vorzugsweise 90 und 350 °C. Vorteilhafterweise wird zu Beginn der SKET-Granulierung eine Startmasse, beispielsweise ein SKET- Granulat aus einem früheren Versuchsansatz, vorgelegt. In der Wirbelschicht verdampft das Wasser aus der Aniontensidpaste, wobei angetrocknete bis getrocknete Keime entstehen, die mit weiteren Mengen Aniontensid und dem flüssigen Vorprodukt umhüllt, granuliert und wiederum gleichzeitig getrocknet werden. Das getrocknete Granulat enthält 1 bis 2 Gew.-% Restwasser. In diesem Zusammenhang wird auf die Lehre der Deutschen Patentanmeldungen DE 4303211 A1 und DE 4303176 A1 verwiesen, deren Inhalt hiermit ausdrücklich eingeschlossen wird.A preferred possibility is to subject the aqueous surfactant pastes to so-called SKET granulation. This is to be understood as granulation with simultaneous drying, which is preferably carried out batchwise or continuously in the fluidized bed. Aqueous pastes of anionic surfactants and the liquid precursors can be introduced into the fluidized bed simultaneously or in succession via one or more nozzles. Fluidized bed apparatuses which are preferably used have base plates with dimensions of 0.4 to 5 m. The SKET granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s. The granules are preferably discharged from the fluidized bed via a size classification of the granules. The classification can take place, for example, by means of a sieving device or by means of an opposed air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed. The inflowing air is usually composed of the heated or unheated classifier air and the heated bottom air. The soil air temperature is between 80 and 400, preferably 90 and 350 ° C. A starting mass, for example a SKET granulate from an earlier test batch, is advantageously introduced at the beginning of the SKET granulation. In the fluidized bed, the water evaporates from the anionic surfactant paste, producing dried to dried germs, which are coated with further amounts of anionic surfactant and the liquid precursor, granulated and again dried at the same time. The dried granulate contains 1 to 2% by weight of residual water. In In this connection, reference is made to the teaching of German patent applications DE 4303211 A1 and DE 4303176 A1, the content of which is hereby expressly included.
Ein Vorteil der Granulate besteht darin, daß sie nicht klebrig sind und hohe Schüttdichten im Bereich von 300 bis 1200 und vorzugsweise 500 bis 800 g/l besitzen.An advantage of the granules is that they are not sticky and have high bulk densities in the range from 300 to 1200 and preferably 500 to 800 g / l.
Gewerbliche AnwendbarkeitIndustrial applicability
Die erfindungsgemäß hergestellten Tensidgranulate werden zur Herstellung von oberflächenaktiven Mitteln verwendet. Bei den oberflächenaktiven Mitteln kann es sich um Wasch-, Spül-, Reinigungs-, Wäscheweichspülmittel und kosmetischen Zubereitungen zur Pflege und Reinigung von Haut und Haaren handeln. Vorzugsweise werden sie für die Herstellung von Seifen und Mund- und Zahnpflegemitteln verwendet.The surfactant granules produced according to the invention are used for the production of surface-active agents. The surface-active agents can be detergents, rinsing agents, cleaning agents, fabric softening agents and cosmetic preparations for the care and cleaning of skin and hair. They are preferably used for the manufacture of soaps and oral and dental care products.
Im Sinne der Erfindung können die erfindungsgemäßen Tensidgranulate allein oder in Kombination mit den genannten Tensidgranulaten in Mengen von 0,1 bis 60, vorzugsweise 0,5 bis 45 und insbesondere 0,6 bis 20 Gew.-% - bezogen auf die Zubereitungen und berechnet als Feststoff - in oberflächen-aktiven Mitteln, vorzugsweise Seifen und Mund- und Zahnpflegemitteln, eingesetzt werden. Vorzugsweise werden hierbei 0,1 bis 20, besonders bevorzugt 0,5 bis 15 und insbesondere 0,6 bis 45 Gew.-% der Tensidgranulate - wie oben beschrieben - in Seifen 0,1 bis 20 und insbesondere 0,6 bis 5 Gew.-% der Tensidgranulate in Mund- und Zahnpflegemitteln verwendet. Das Einsatzverhältnis der erfindungsgemäßen Tensidgranulats und der genannten Tensidgranulate untereinander kann 20 : 80 bis 80 : 20, vorzugsweise 30 : 70 bis 70 : 30 und insbesondere 40 : 60 bis 60 : 40 Gewichtsteile betragen.For the purposes of the invention, the surfactant granules according to the invention, alone or in combination with the surfactant granules mentioned, in amounts of 0.1 to 60, preferably 0.5 to 45 and in particular 0.6 to 20% by weight, based on the preparations and calculated as Solid - can be used in surface-active agents, preferably soaps and oral and dental care products. Preferably 0.1 to 20, particularly preferably 0.5 to 15 and in particular 0.6 to 45% by weight of the surfactant granules - as described above - in soaps 0.1 to 20 and in particular 0.6 to 5% by weight. -% of the surfactant granules used in oral and dental care products. The use ratio of the surfactant granules according to the invention and the surfactant granules mentioned to one another can be 20:80 to 80:20, preferably 30:70 to 70:30 and in particular 40:60 to 60:40 parts by weight.
Wasch-, Spül und ReinigungsmittelWashing, rinsing and cleaning agents
Neben den erfindungsgemäßen Granulaten können die Wasch-, Spül und Reinigungsmittel noch weitere typische Inhaltsstoffe, wie beispielsweise anionische Tenside, nichtionische Tenside, Builder, Bleichmittel, Bleichaktivatoren, Waschkraftverstärker, Enzyme, Enzymstabilisatoren, Vergrauungsinhibitoren, optische Aufheller, Soil repeliants, Schauminhibitoren, anorganische Salze sowie Duft- und Farbstoffe enthalten. Kosmetischen ZubereitungenIn addition to the granules according to the invention, the washing, rinsing and cleaning agents can also contain other typical ingredients, such as, for example, anionic surfactants, nonionic surfactants, builders, bleaching agents, bleach activators, detergency boosters, enzymes, enzyme stabilizers, graying inhibitors, optical brighteners, soil repeliants, foam inhibitors, and inorganic salts Contain fragrances and dyes. Cosmetic preparations
Die erfindungsgemäßen Tensidgemische können zur Herstellung von kosmetischen Zubereitungen, wie beispielsweise Haarshampoos, Haarlotionen, Schaumbäder, Duschbäder, Cremes, Gele, Lotionen, Emulsionen, Wachs/Fett-Massen, Stiftpräparate oder Puder dienen. Diese Mittel können ferner als weitere Hilfs- und Zusatzstoffe milde Tenside, Ölkörper, Emulgato- ren, Überfettungsmittel, Perlglanzwachse, Konsistenzgeber, Verdickungsmittel, Polymere, Siliconverbindungen, Fette, Wachse, Stabilisatoren, biogene Wirkstoffe, Deowirkstoffe, Antischuppenmittel, Filmbildner, Quellmittel, UV-Lichtschutzfaktoren, Antioxidantien, Hydrotrope, Konservierungsmittel, Insektenrepellentien, Selbstbräuner, Solubilisatoren, Parfümöle, Farbstoffe, keimhemmende Mittel und dergleichen enthalten.The surfactant mixtures according to the invention can be used to produce cosmetic preparations, such as, for example, hair shampoos, hair lotions, foam baths, shower baths, creams, gels, lotions, emulsions, wax / fat compositions, stick preparations or powder. These 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, stabilizers, biogenic agents, deodorant agents, antidandruff agents, film formers, swelling agents, UV agents. Contain sun protection factors, antioxidants, hydrotropes, preservatives, insect repellents, self-tanners, solubilizers, perfume oils, dyes, germ-inhibiting agents and the like.
Die Stückseifen, vorzugsweise Syndetseifen, können als Gerüststoffe wasserlösliche bzw. in Wasser quellende Strukturanten, wie beispielsweise Stärke, vorzugsweise Weizen- oder Maisstärke aufweisen. Als Builder können sie ferner feinteilige, wasserunlösliche Alkalialuminiumsilicate enthalten, wobei die Verwendung von synthetischen, gebundenes Wasser enthaltender kristalliner Natriumalumosilicate und hierbei insbesondere von Zeolith A besonders bevorzugt ist; Zeolith NaX sowie dessen Mischungen mit Zeolith NaA können ebenfalls eingesetzt werden. Geeignete Zeolithe besitzen ein Calciumbindevermögen im Bereich von 100 bis 200 mg CaO/g. Als flüssige Builder können auch NTA und/oder EDTA eingesetzt werden. Als Plastifikatoren (Plasticiser) kommen Fettalkohole, Fettsäurepartialglyceride oder Wachsester mit jeweils 12 bis 22 Kohlenstoffatomen in den Fettresten in Frage.The bar soaps, preferably syndet soaps, can have water-soluble or water-swelling structurants as builders, such as starch, preferably wheat or corn starch. As builders, they can also contain finely divided, water-insoluble alkali aluminum silicates, the use of synthetic, bound water-containing crystalline sodium aluminosilicates and in this case particularly of zeolite A being particularly preferred; Zeolite NaX and its mixtures with zeolite NaA can also be used. Suitable zeolites have a calcium binding capacity in the range from 100 to 200 mg CaO / g. NTA and / or EDTA can also be used as liquid builders. Suitable plasticizers are fatty alcohols, fatty acid partial glycerides or wax esters, each with 12 to 22 carbon atoms in the fat residues.
Mund- und ZahnpfleqemittelOral and dental care products
Die erfindungsgemäßen Tensidgranulate können zur Herstellung von Mund- und Zahnpflegemitteln eingesetzt werden. Die Mittel können ferner als weitere Hilfs- und Zusatzstoffe Schleif- und Poliermittel, Aromakomponenten, Chitosane und andere typische Inhaltsstoffe für Zahnpasten enthalten.The surfactant granules according to the invention can be used for the production of oral and dental care products. The agents may also contain abrasives and polishes, aroma components, chitosans and other typical ingredients for toothpastes as further auxiliaries and additives.
Als Schleif- und Poliermittel können die erfindungsgemäßen Mittel Kreide, Dicalciumphosphat, Natriumbicarbonat, Natriumsulfat, unlösliches Natriummetaphosphat, Aluminiumsilicat, Schichtsilicate, Hydrotalcite, Calciumpyrophosphat, feinteilige Kunstharze, Kieselsäuren, Aluminiumoxid, Aluminiumoxidtrihydrat, Talkum, Zeolithe, Magnesiumaluminiumsilicat (Veegum®), Calciumsulfat, Magnesiumcarbonat und/oder Magnesiumoxid enthalten. Der Anteil der Schleif- und Poliermittel kann 1 bis 25, vorzugsweise 10 bis 20 Gew.-% - bezogen auf die fertigen Zubereitungen - betragen.As grinding and polishing agents, the agents according to the invention can be chalk, dicalcium phosphate, sodium bicarbonate, sodium sulfate, insoluble sodium metaphosphate, aluminum silicate, layer silicates, hydrotalcites, calcium pyrophosphate, fine-particle synthetic resins, silicas, aluminum oxide, aluminum oxide trihydrate, talc, zeolites, calcium aluminum sulfate, magnesium aluminum sulfate and / or contain magnesium oxide. The share of grinding and Polishing agent can be 1 to 25, preferably 10 to 20% by weight, based on the finished preparations.
Neben den genannten Tensiden kommen als weitere Hilfs- und Zusatzstoffe auch Aromakomponenten in Frage, beispielsweise Pfefferminzöl, Krauseminzöl, Anisöl, Sternanisöl, Kümmelöl, Eukalyptusöl, Fenchel, Zimtöl, Nelkenöl, Geraniumöl, Salbeiöl, Pimentöl, Thymianöl, Majoranöl, Basilikumöl, Citrusöl, Gaultheriaöl oder eine oder mehrere daraus isolierte oder synthetisch erzeugte Komponenten dieser Öle, wie z.B. Menthol, Carvon, Anethol, Cineol, Eugenol, Zimtaldehyd, Cargophyllen, Geraniol, Citronellol, Linalool, Salven, Thymol, Terpinan, Terpinol, Methylchavicol und Methylsalicylat. Weitere geeignete Aromen sind z.B. Methylacetat, Vanillin, lonone, Linalylacetat, Rhodinol und Piperiton. Als Süßungsmittel eignen sich entweder natürliche Zucker wie Sucrose, Maltose, Lactose und Fructose oder synthetische Süßstoffe wie z.B. Saccharin-Natriumsalz, Natriumcyclamat oder Aspartam. Der Anteil der Aromastoffe kann 0 bis 3, vorzugsweise 1 bis 2 Gew.-% - bezogen auf die fertigen Zubereitungen - betragen.In addition to the surfactants mentioned, other auxiliary substances and additives are also flavor components, for example peppermint oil, spearmint oil, anise oil, star anise oil, caraway oil, eucalyptus oil, fennel, cinnamon oil, clove oil, geranium oil, sage oil, allspice oil, thyme oil, marjoram oil, basil oil, citrus oil or one or more components of these oils isolated or synthetically produced, such as Menthol, carvone, anethole, cineol, eugenol, cinnamaldehyde, cargophylls, geraniol, citronellol, linalool, salves, thymol, terpinan, terpinol, methylchavicol and methyl salicylate. Other suitable flavors are e.g. Methyl acetate, vanillin, lonone, linalyl acetate, rhodinol and piperiton. Either natural sugars such as sucrose, maltose, lactose and fructose or synthetic sweeteners such as e.g. Saccharin sodium salt, sodium cyclamate or aspartame. The proportion of the flavoring substances can be 0 to 3, preferably 1 to 2% by weight, based on the finished preparations.
Chitosane stellen Biopolymere dar und werden zur Gruppe der Hydrokolloide gezählt. Chemisch betrachtet handelt es sich um partiell deacetylierte Chitine unterschiedlichen Molekulargewichtes, die den folgenden - idealisierten - Monomerbaustein enthalten:Chitosans are biopolymers and belong to the group of hydrocolloids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit:
Im Gegensatz zu den meisten Hydrokolloiden, die im Bereich biologischer pH-Werte negativ geladen sind, stellen Chitosane unter diesen Bedingungen kationische Biopolymere dar. Die positiv geladenen Chitosane können mit entgegengesetzt geladenen Oberflächen in Wechselwirkung treten und werden daher in kosmetischen Haar- und Körperpflegemitteln sowie pharmazeutischen Zubereitungen eingesetzt (vgl. Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, S. 231-332). Übersichten zu diesem Thema sind auch beispielsweise von B.Gesslein et al. in HAPPI 27, 57 (1990), O.Skaugrud in Drug Cosm.lnd. 148, 24 (1991) und E.Onsoyen et al. in Seifen-Öle-Fette-Wachse 117, 633 (1991) erschienen. Zur Herstellung der Chitosane geht man von Chitin, vorzugsweise den Schalenresten von Krustentieren aus, die als billige Rohstoffe in großen Mengen zur Verfügung stehen. Das Chitin wird dabei in einem Verfahren das erstmals von Hackmann et al. beschrieben worden ist, üblicherweise zunächst durch Zusatz von Basen deproteiniert, durch Zugabe von Mineralsäuren demineralisiert und schließlich durch Zugabe von starken Basen deacetyliert, wobei die Molekulargewichte über ein breites Spektrum verteilt sein können. Entsprechende Verfahren sind beispielsweise aus Makromol. Chem. 177, 3589 (1976) oder der französischen Patentanmeldung FR 2701266 A bekannt. Vorzugsweise werden solche Typen eingesetzt, wie sie in den deutschen Patentanmeldungen DE 4442987 A1 und DE 19537001 A1 (Henkel) offenbart werden, und die ein durchschnittliches Molekulargewicht von 800.000 bis 1.200.000 Dalton, eine Viskosität nach Brookfield (1 gew.-%ig in Glycolsäure) unterhalb von 5000 mPas, einen Deacetylierungsgrad im Bereich von 80 bis 88 % und einem Aschegehalt von weniger als 0,3 Gew.-% aufweisen. Neben den Chitosanen als typischen kationischen Biopolymeren kommen im Sinne der Erfindung auch anionisch bzw. nichtionisch derivatisierte Chitosane, wie z.B. Carboxylierungs-, Succinylierungs- oder Alkoxylierungsprodukte in Frage, wie sie beispielsweise in der deutschen Patentschrift DE 3713099 C2 (L'Oreal) sowie der deutschen Patentanmeldung DE 19604180 A1 (Henkel) beschrieben werden. Der Anteil an Chitosanen kann 0 bis 2, vorzugsweise 0,1 bis 0,5 Gew.-% - bezogen auf die fertigen Zubereitungen - betragen.In contrast to most hydrocolloids, which are negatively charged in the range of biological pH values, chitosans are cationic biopolymers under these conditions. The positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and body care products and pharmaceuticals Preparations used (cf. Ullmann 's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pp. 231-332). Overviews on this topic have also been published, for example, by B. Gesslein et al. in HAPPI 27, 57 (1990), O.Skaugrud in Drug Cosm. Ind. 148: 24 (1991) and E. Onoyen et al. in Seifen-Öle-Fette-Wwachs 117, 633 (1991). The production of chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials. The chitin is used in a process that was first developed by Hackmann et al. has been described Usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacetylated by adding strong bases, the molecular weights being able to be distributed over a broad spectrum. Appropriate methods are, for example, made from Makromol. Chem. 177, 3589 (1976) or French patent application FR 2701266 A. Those types are preferably used, as are disclosed in German patent applications DE 4442987 A1 and DE 19537001 A1 (Henkel), which have an average molecular weight of 800,000 to 1,200,000 Daltons, a Brookfield viscosity (1% by weight in Glycolic acid) below 5000 mPas, a degree of deacetylation in the range from 80 to 88% and an ash content of less than 0.3% by weight. In addition to the chitosans as typical cationic biopolymers, anionically or nonionically derivatized chitosans, such as, for example, carboxylation, succinylation or alkoxylation products, as described, for example, in German patent DE 3713099 C2 (L'Oreal) and in German, are also suitable for the purposes of the invention Patent application DE 19604180 A1 (Henkel) can be described. The proportion of chitosans can be 0 to 2, preferably 0.1 to 0.5% by weight, based on the finished preparations.
Ferner kommen für den Einsatz insbesondere in Zahnpasten als weitere Hilfs- und Zusatzstoffe Feuchthaltemittel wie z.B. Sorbit, Glycerin oder Polyethylenglycole, Konsistenzregler, desodorierende Wirkstoffe, Quellstoffe und Bindemittel, wie z.B. Carboxymethylcellulose oder Xanthan Gum, Wirkstoffe gegen Mund- und Zahnerkrankungen, wasserlösliche Fluorverbindungen wie z.B. Natriumfluorid oder Natriummonofluorphosphat in Betracht.Furthermore, humectants such as e.g. Sorbitol, glycerin or polyethylene glycols, consistency regulators, deodorising agents, swelling agents and binders, such as e.g. Carboxymethyl cellulose or xanthan gum, active substances against mouth and tooth diseases, water-soluble fluorine compounds such as Sodium fluoride or sodium monofluorophosphate.
Der Anteil der Hilfs- und Zusatzstoffe insgesamt ist an sich unkritisch und richtet sich nach der Art des schließlich zu konfektionierenden Mittels. Üblicherweise wird der Anteil 5 bis 98 und vorzugsweise 80 bis 90 Gew.-% - bezogen auf die fertigen Zubereitungen - betragen.The proportion of auxiliaries and additives overall is not critical per se and depends on the type of agent that is ultimately to be assembled. The proportion will usually be 5 to 98% by weight and preferably 80 to 90% by weight, based on the finished preparations.
Eine typische Zahnpaste weist im Sinne eines weiteren Gegenstandes der Erfindung folgende typische Zusammensetzung auf (Wasser ad 100 Gew.-%):A typical toothpaste has the following typical composition (water ad 100% by weight):
(a) 0,1 bis 20, vorzugsweise 0,6 bis 5 Gew.-% Tensidgranulate,(a) 0.1 to 20, preferably 0.6 to 5% by weight of surfactant granules,
(b) 1 bis 25, vorzugsweise 10 bis 20 Gew.-% Schleif- und Poliermittel,(b) 1 to 25, preferably 10 to 20% by weight of abrasive and polishing agents,
(c) 0 bis 65, vorzugsweise 10 bis 45 Gew.-% Feuchthaltemittel,(c) 0 to 65, preferably 10 to 45% by weight of humectant,
(d) O bis 2, vorzugsweise 0,1 bis 0,5 Gew.-% Chitosane(d) 0 to 2, preferably 0.1 to 0.5% by weight of chitosans
(e) 0 bis 3, vorzugsweise 1 bis 2 Gew.-% Aromastoffe und(e) 0 to 3, preferably 1 to 2% by weight of flavorings and
(f) 0 bis 5, vorzugsweise 1 bis 3 Gew.-% weitere Hilfsstoffe,(f) 0 to 5, preferably 1 to 3% by weight of further auxiliaries,
mit der Maßgabe, daß sich die Einsatzmengen zu 100 Gew.-% ergänzen. Beispielewith the proviso that the amounts used add up to 100% by weight. Examples
In den Beispielen 1 und 2 wurden entsprechend der Lehre der EP 0319819 A1 ein saurer Schwefelsäurehalbester des Kokosmonoglycerids (KMGSS) über eine Mehrstoffdüse mit 50 gew.- %iger Natronlauge sprühneutralisiert (Treibgas: Ammoniak) und direkt in einer Anlage zur Granuliertrocknung (AGT) der Firma Glatt (BRD) getrocknet und gleichzeitig granuliert. Als Startmasse wurde jeweils ein Tensidgranulat eingesetzt, das bei einem vorangegangenen Ansatz (unter denselben Verfahrensbedingungen) hergestellt worden war und in etwa dieselbe Zusammensetzung besaß wie die fertigen Granulate der Beispiele 1 und 2. Die Verfahrensbedingungen können der Tabelle 1 entnommen werden.In Examples 1 and 2, an acidic sulfuric acid half-ester of coconut monoglyceride (KMGSS) was spray-neutralized using a multi-component nozzle with 50% by weight sodium hydroxide solution (propellant gas: ammonia) and directly in a plant for granulation drying (AGT) according to the teaching of EP 0319819 A1 Glatt (Germany) dried and granulated at the same time. In each case, a surfactant granulate was used as starting mass, which had been produced in a previous batch (under the same process conditions) and had approximately the same composition as the finished granules of Examples 1 and 2. The process conditions can be found in Table 1.
In beiden Beispielen wurden staubfreie und nicht klebende Granulate mit hohen Tensidanteilen erhalten (siehe Tabelle 2). Der Anteil der Granulate mit einer Korngröße oberhalb von 2,5 mm lag in allen Beispielen unter 5 Gew.%.In both examples, dust-free and non-sticky granules with high surfactant contents were obtained (see Table 2). The proportion of the granules with a grain size above 2.5 mm was below 5% by weight in all examples.
Tabelle 1 VerfahrensparameterTable 1 Process parameters
Tabelle 2Table 2
Kenndaten der Produkte Characteristics of the products
Die Tensidgemische wurden in eine Standard-Zahnpastenrezeptur eingesetzt. Das Schaumvermögen wurde gemäß der Reibschaummethode in einem EHMEDA-Reibschaumgerät bestimmt [Fette, Seifen, Anstrichmitt. 66, 955 (1964)]. Hierzu wurden 20 g Zahnpaste in 180 g Wasser dispergiert und im Schaumzylinder auf 45°C erwärmt. Dort wurde durch 60 s Reibung mit einer vertikal rotierenden Perlonbürste bei 2600 UpM an einem zylindrisch geformten Metalldrahtgitter Schaum erzeugt. In Tabelle 1 ist das Schaumvolumen 0,5 min nach Beendigung der Schaumerzeugung aufgeführt. Die Beurteilung der Reinigungsleitung erfolgte nach dem Zähneputzen durch 5 unabhängige Testpersonen nach folgenden Kriterien: (++) = sehr gute Reinigung durch Abrasivstoffe; (+) = gute bis befreidigende Reinigung durch Abrasivstoffe. Die Beispiele 1 bis 3 in Tabelle 1 sind erfindungsgemäß, die Beispiele V1 bis V3 dienen zum Vergleich.The surfactant mixtures were used in a standard toothpaste formulation. The foaming power was determined according to the friction foam method in an EHMEDA friction foam device [greases, soaps, paints. 66, 955 (1964)]. For this purpose, 20 g of toothpaste were dispersed in 180 g of water and heated to 45 ° C. in the foam cylinder. There, 60 seconds of friction with a vertically rotating Perlon brush at 2600 rpm generated foam on a cylindrically shaped metal wire mesh. Table 1 shows the foam volume 0.5 min after the end of foam generation. After cleaning the teeth, the cleaning line was assessed by 5 independent test persons according to the following criteria: (++) = very good cleaning with abrasives; (+) = good to liberating cleaning with abrasives. Examples 1 to 3 in Table 1 are according to the invention, Examples V1 to V3 serve for comparison.
Tabelle 1Table 1
Beurteilung von Zahnpasten (Mengenangaben als Gew.-%)Assessment of toothpastes (quantities as% by weight)
Auf Basis der nachfolgenden erfindungsgemäßen Rezepturen 1 bis 3 sowie der Vergleichsrezepturen V1 und V2 wurden Seifenstücke gepreßt und auf ihre anwendungs-technischen Eigenschaften (Bewertung auf einer Skala von - ausreichend, + = befriedigend, ++ = gut bis +++ = sehr gut) untersucht. Die Ergebnisse sind in Tabelle 2 zusammengefaßt. Nach allen Testkriterien zeigt die erfindungsgemäße Formulierung deutliche Vorteile auf. So zeichnen sich Stückseifen mit Monoglycerid(ether)sulfat-Granulaten gegenüber dem Ver-gleichsbeispielen 1 und 2, durch eine geringere Tendenz zur Wasseraufnahme bzw. Versumpfungsneigung, eine höhere Stabilität und besseres Schaumvermögen aus. On the basis of the following recipes 1 to 3 according to the invention and the comparative recipes V1 and V2, soap bars were pressed and their application properties (evaluation on a scale from - sufficient, + = satisfactory, ++ = good to +++ = very good) examined. The results are summarized in Table 2. According to all test criteria, the formulation according to the invention shows clear advantages. Bar soaps with monoglyceride (ether) sulfate granules are distinguished from comparative examples 1 and 2 by a lower tendency to absorb water or tend to sump, higher stability and better foaming power.
Tabelle 2:Table 2:
Stückseifen • Zusammensetzungen und Eigenschaften (Mengenangaben als Gew.-%)Bar soaps • Compositions and properties (quantities as% by weight)

Claims

Patentansprüche claims
1. Tensidgranulate, dadurch erhältlich, daß man 20 bis 60 Gew.-%ige wäßrige Pasten enthaltend Monoglycerid(ether)sulfate einer Trocknung unter gleichzeitiger Granulierung in der Wirbelschicht unterwirft.1. surfactant granules, obtainable by subjecting 20 to 60% by weight aqueous pastes containing monoglyceride (ether) sulfates to drying with simultaneous granulation in the fluidized bed.
2. Tensidgranulate nach Anspruch 1 , dadurch gekennzeichnet, daß man Monoglycerid(ether)- sulfate der Formel (I) einsetzt,2. surfactant granules according to claim 1, characterized in that one uses monoglyceride (ether) sulfates of the formula (I),
CH2θ(CH2CH20)x-COR1 CH2θ (CH 2 CH 2 0) x-COR 1
I CH-0(CH2CH20)yHI CH-0 (CH 2 CH 2 0) y H
(0(0
I CH20(CH2CH2θ)z-S03XI CH 2 0 (CH 2 CH2θ) z -S0 3 X
in der R1CO für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, x, y und z in Summe für 0 oder für Zahlen von 1 bis 30 und X für ein Alkali- oder Erdalkalimetall steht.in which R 1 CO stands for a linear or branched acyl radical with 6 to 22 carbon atoms, x, y and z in total for 0 or for numbers from 1 to 30 and X for an alkali or alkaline earth metal.
3. Tensidgranulate nach den Ansprüchen 1 und/oder 2, dadurch gekennzeichnet, daß man Monoglycerid(ether)sulfate der Formel (I) einsetzt, in der R1CO für einen linearen Acylrest mit 12 bis 14 Kohlenstoffatomen, x, y und z für 0 und X für Natrium steht.3. surfactant granules according to claims 1 and / or 2, characterized in that one uses monoglyceride (ether) sulfates of the formula (I) in which R 1 CO for a linear acyl radical having 12 to 14 carbon atoms, x, y and z for 0 and X stands for sodium.
4. Tensidgranulate nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß wäßrige Pasten getrocknet und granuliert werden, die als weitere Tenside Fettalkoholsulfate, Sulfosuccinate, Olefinsulfonate, Alkyl- und/oder Alkenyloligoglykoside enthalten.4. surfactant granules according to at least one of claims 1 to 3, characterized in that aqueous pastes are dried and granulated, which contain as further surfactants fatty alcohol sulfates, sulfosuccinates, olefin sulfonates, alkyl and / or alkenyl oligoglycosides.
5. Tensidgranulate nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie in Mischung mit Granulaten von Fettalkoholsulfaten, Sulfosuccinaten, Olefin- sulfonaten, Alkyl- und/oder Alkenyloligoglykosiden vorliegen.5. surfactant granules according to at least one of claims 1 to 4, characterized in that they are present in a mixture with granules of fatty alcohol sulfates, sulfosuccinates, olefin sulfonates, alkyl and / or alkenyl oligoglycosides.
6. Tensidgranulate nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß sie Monoglycerid(ether)sulfate und die weiteren Tenside im Gewichtsverhältnis 20:80 bis 80:20 enthalten. 6. surfactant granules according to at least one of claims 1 to 5, characterized in that they contain monoglyceride (ether) sulfates and the other surfactants in a weight ratio of 20:80 to 80:20.
7. Verwendung von Tensidgranulaten nach mindestens einem der Ansprüche 1 bis 6 zur Herstellung von oberflächenaktiven Mitteln.7. Use of surfactant granules according to at least one of claims 1 to 6 for the production of surface-active agents.
8. Verwendung von Tensidgranulaten nach Anspruch 7, dadurch gekennzeichnet, daß man sie zur Herstellung von Mund- und Zahnpflegemitteln einsetzt.8. Use of surfactant granules according to claim 7, characterized in that they are used for the manufacture of oral and dental care products.
9. Verwendung von Tensidgranulaten nach Anspruch 7, dadurch gekennzeichnet, daß man sie zur Herstellung von Seifen einsetzt.9. Use of surfactant granules according to claim 7, characterized in that they are used for the production of soaps.
10. Mund- und Zahnpflegemittel enthaltend10. Containing oral and dental care products
(a) 0,1 bis 20 Gew.-% Tensidgranulate nach mindestens einem der Ansprüche 1 bis 6,(a) 0.1 to 20% by weight of surfactant granules according to at least one of claims 1 to 6,
(b) 1 bis 25 Gew.-% Schleif- und Poliermittel,(b) 1 to 25% by weight of abrasive and polishing agents,
(c) 0 bis 65 Gew.-% Feuchthaltemittel,(c) 0 to 65% by weight humectant,
(d) O bis 2 Gew.-% Chitosane,(d) 0 to 2% by weight of chitosans,
(e) 0 bis 3 Gew.-% Aromastoffe und(e) 0 to 3% by weight of flavorings and
(f) O bis 5 Gew.-% weitere Hilfsstoffe(f) 0 to 5% by weight of other auxiliaries
mit der Maßgabe, daß sich die Einsatzmengen zu 100 Gew.-% ergänzen. with the proviso that the amounts used add up to 100% by weight.
EP00914104A 1999-03-12 2000-03-03 Method for producing surfactant granulates Withdrawn EP1161519A1 (en)

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