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EP0614484A1 - Powdery surface-active agent mixture. - Google Patents

Powdery surface-active agent mixture.

Info

Publication number
EP0614484A1
EP0614484A1 EP92923773A EP92923773A EP0614484A1 EP 0614484 A1 EP0614484 A1 EP 0614484A1 EP 92923773 A EP92923773 A EP 92923773A EP 92923773 A EP92923773 A EP 92923773A EP 0614484 A1 EP0614484 A1 EP 0614484A1
Authority
EP
European Patent Office
Prior art keywords
weight
alkyl
alkali
formula
carrier material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP92923773A
Other languages
German (de)
French (fr)
Other versions
EP0614484B1 (en
Inventor
Martina Kihn-Botulinski
Hubert Freese
Eric Sung
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0614484A1 publication Critical patent/EP0614484A1/en
Application granted granted Critical
Publication of EP0614484B1 publication Critical patent/EP0614484B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D1/66—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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • 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 powdered, pourable and free-flowing surfactant mixtures which contain alkyl sulfate, alkyl glycoside and inorganic carrier material, a process for their preparation and their use as premixes for the production of particulate detergents and cleaners.
  • Preferred surfactants are anionic surfactants, especially those of the alkylbenzenesulfonate type, and nonionic surfactants, especially ethoxylated fatty alcohols.
  • the water is preferably removed from the slurry by spray drying.
  • alkylbenzenesulfonate in detergents and cleaning agents has recently been called into question because of the petroleum base of this surfactant.
  • sulfation products of compounds accessible from renewable raw materials, in particular fatty alcohols come into consideration as more environmentally compatible surfactants with comparable good cleaning properties.
  • aqueous slurries containing alkylbenzenesulfonate can be spray-dried without problems at the temperatures customary in such processes, normally about 250 ° C. to 350 ° C., there is a risk with aqueous slurries which contain comparable amounts of other surfactants, in particular alkyl sulfates self-ignition.
  • the object was therefore to develop a process which allows the preparation of powdered surfactant mixtures free from alkylbenzenesulfonate by spray drying an aqueous surfactant-containing slurry, without the self-ignition of the spray drying product occurring during production, the powdered products being free-flowing and free-flowing should.
  • R * is an alkyl radical having 10 to 20 C atoms and X is an alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion, an amount of 1 to 5 parts by weight of alkylglycoside of the formula
  • R 1 is an alkyl radical having 8 to 22 carbon atoms
  • G is a glycose unit and n is a number from 1 to 10
  • the weight ratio of alkyl sulfate to alkyl glycoside being 8: 1 to 1: 1, preferably 5: 1 to 2: 1 , be ⁇ , and an amount of 20 to 100 parts by weight of an essentially inorganic phosphate-free carrier material which contains alkali carbonate and alkali alumosilicate in a weight ratio of 2: 1 to 1: 3, with as much Water mixes that a flowable and pumpable mixture at temperatures below 95 ° C with a viscosity of 3000 mPa-s to 15000 mPa-s, measured at 60 ° C to 95 ° C, is formed, and this by spray drying using drying gases Temperatures below 250 ° C withdraw the water to such an extent that a powdery, free-flowing product is formed.
  • the water content in the powder product is not more than 20% by weight, in particular from 5% by weight to 15% by weight.
  • the residual water content relates to the free water not bound in the crystal lattice.
  • the process is preferably carried out in such a way that 3 to 10 parts by weight of alkyl sulfate according to formula I, 2 to 3 parts by weight of alkyl glycoside according to formula II and 25 to 80 parts by weight of the inorganic carrier material are mixed with so much water that at least 35 % By weight, in particular 40% by weight to 50% by weight of water, is formed.
  • the phosphate-free, essentially inorganic carrier material preferably consists of 40% by weight to 60% by weight of alkali alumosilicate, in particular zeolite NaA and / or NaX, 20% by weight to 40% by weight of alkali carbonate, up to 20% by weight of other inorganic salts, in particular alkali silicates, alkali hydrogen carbonates and / or alkali chlorides, and not more than 20% by weight of organic material, in particular alkali polycarboxylate.
  • the further inorganic salts mentioned are contained in the carrier material in particular in amounts of 1% by weight to 10% by weight, the carrier material being free from alkali silicate with a molar ratio of SiO 2 to alkali oxide up to 2 and the proportion of Alkali silicate with a molar ratio of SiO 2 to alkali oxide over 2 is not more than 5% by weight, in each case based on the total support material.
  • the carrier material is preferably also free of alkali sulfates.
  • Alumosilicates suitable in the context of the invention have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • the polycarboxylates mentioned are known cobuilder substances in the form polymeric polycarboxylic acids or their water-soluble salts, in particular alkali salts, which can be obtained by polymerizing acrylic acid, methacrylic acid and / or maleic acid monomers or their salts. Such substances are preferably contained in the carrier material in amounts of from 1% by weight to 15% by weight, in particular from 5% by weight to 13% by weight, based in each case on the entire carrier material.
  • the preferred alkali metal for all of the ingredients mentioned is sodium.
  • spray towers in the upper part of which the slurry is sprayed into fine droplets by pressure nozzles, which move under the action of gravity into the lower part of the spray tower and come into contact with hot drying gases which are guided in cocurrent or preferably in countercurrent to the particles to be dried. It is important to ensure that the temperature of the drying gases is not so high that the temperature of the spray-dried particles rises above the self-ignition temperature of these particles.
  • aqueous, generally 30 to 60% by weight alkyl glycoside pastes as are usually obtained in the context of alkyl glycoside production and, if appropriate, subsequent bleaching.
  • the alkyl sulfate component and in particular the carrier component can be used as an aqueous solution or slurry.
  • at least about 35% by weight, preferably 40 up to 50% by weight of water is present in the slurry to be dried.
  • the powdery, pourable and free-flowing surfactant mixtures according to the invention produced by the process according to the invention preferably contain 10% by weight to 30% by weight of alkyl sulfate of the formula I,
  • R * is an alkyl radical having 10 to 20 carbon atoms and X is an alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion, 2% by weight to 10% by weight of alkyl glycoside of the formula II,
  • R2 is an alkyl radical having 8 to 22 carbon atoms
  • G is a glycose unit
  • n is a number from 1 to 10, the weight ratio of
  • Alkyl sulfate to alkyl glycoside is 8: 1 to 1: 1,
  • an essentially inorganic carrier material which contains alkali carbonate and alkali alumosilicate in a weight ratio
  • Suitable alkyl sulfates for use in the alkylbenzenesulfonate-free surfactant mixtures according to the invention are the compounds of the formula I in which R * is an alkyl radical having 10 to 20 C atoms and X is an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion Question.
  • R * is an alkyl radical having 10 to 20 C atoms
  • X is an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion Question.
  • the derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable.
  • the alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or Chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a conventional sulfating reagent in particular sulfur trioxide or Chlorosulfonic acid
  • alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases are contained in the powders according to the invention preferably in amounts of 10% by weight to 30% by weight, in particular 12% by weight to 25% by weight.
  • alkyl glycosides suitable for incorporation into the surfactant mixtures according to the invention are compounds of the general formula II in which R 1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10.
  • R 1 is an alkyl radical having 8 to 22 carbon atoms
  • G is a glycose unit
  • n is a number between 1 and 10.
  • the glycoside component ((G) n in formula II) of such alkyl glycosides are oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, alt ⁇ rose, allose, idose, ribose, arabinose, xylose and lyxose belong.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization.
  • the degree of oligomerization (n in formula II) generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the alkyl glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because of its good availability.
  • the alkyl part (R 2 in formula II) of the alkyl glycosides contained in the surfactant mixtures according to the invention preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, are also suitable for the production of alkyl glycosides can be used. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octa-decyl radicals and mixtures thereof are particularly useful.
  • the alkyl glycosides can be contain small amounts, for example 1 to 2%, of unreacted free fatty alcohol, which does not have a disadvantageous effect on the properties of the powder products produced therewith.
  • alkyl glycosides are contained in the surfactant mixtures according to the invention in amounts of 2% by weight to 10% by weight, preferably 3% by weight to 8% by weight, the weight ratio of alkyl sulfate to alkyl glycoside being 8: 1 to 1: 1, preferably 5: 1 to 2: 1.
  • the mixtures according to the invention can contain other surfactants, preferably nonionic surfactants and / or anionic surfactants and, in particular, fatty acid soaps with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and surfactants of the sulfate or sulfonate type preferably not more than 5% by weight, in particular from 0.1% by weight to 3% by weight, based in each case on the total surfactant preparation.
  • the sulphated alkoxylation products of the alcohols mentioned, so-called ether sulphates belong to the additionally usable surfactants of the sulphate type.
  • Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants also include the oc-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms -Atoms, preferably 1 to 4 carbon atoms, derived sulfonation products.
  • the nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of alkoxylation of the alcohols is between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • the derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used.
  • the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals are particularly useful as well as their mixtures.
  • Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl moiety can also be used.
  • the preparations according to the invention can contain small amounts, preferably not more than 5% by weight in total, of further constituents which are customary in washing and cleaning agents and are stable under the spray drying conditions.
  • these optional constituents include, in particular, complex biiners for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, graying inhibitors, for example cellulose ethers, foam inhibitors, for example organopolysiloxanes or paraffins, and optical brighteners, for example stilbene derivative disulphons.
  • the inventive surfactant mixtures do not contain more than 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4'-bis (2, 4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, not more than 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, not more than 3% by weight, in particular 0.5% by weight to 2% by weight, of graying inhibitors and not more than 2% by weight, in particular 0.1% by weight to 1% by weight, of foam inhibitor Contain bitters, the weight percentages referring to the entire surfactant mixture.
  • optical brighteners in particular compounds from the class of the substituted 4,4'-bis (2, 4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, not more
  • the powdered surfactant mixtures according to the invention are used in particular as pourable and free-flowing precursors for the production of particulate detergents or cleaning agents.
  • the powders according to the invention should have average grain sizes of preferably 0.2 mm to 0.4 mm and should be largely free of particles with diameters of more than 2 mm or less than 50 ⁇ m. These limits are normally met by the surfactant mixtures obtained by spray drying, otherwise particles outside this size range can be removed by simple sieving and used in the manufacturing process. development process.
  • the bulk density of the powder products according to the invention is preferably between 400 and 600 grams per liter. If desired, their liter weight can be increased in principle by conventional densification, if they are to be used for the production of detergents or cleaning agents with a high liter weight, so-called heavy powders.
  • the preparations according to the invention are free-flowing, free-flowing powders which do not lose their advantageous properties even after prolonged storage. They are also lightening-free, light-colored, have an acceptable odor and show no tendency to jam. In contrast, strong clumping was found in powders which contained the same amounts of alkylbenzenesulfonate instead of alkyl sulfate. Products of this type were also unacceptably colored brown, even if they contained only relatively small amounts of alkyl glycoside, for example 3% by weight or less. All the more surprising are the unexpectedly positive properties of the surfactant mixtures according to the invention.
  • the surfactant mixtures according to the invention can be mixed in a manner known in principle with other constituents in the form of powder or powder which are customary in such agents, in particular bleaching agents, bleach activators, enzymes, foam inhibitors, optical brighteners, Graying inhibitors, for example cellulose ethers and abrasives, for example quartz powder, belong.
  • the spraying of liquid, liquefied or dissolved ingredients, for example liquid enzymes, dyes, fragrances or other surfactants, in particular nonionic surfactants, onto the powders according to the invention is also possible in a known manner.
  • the surfactant mixtures according to the invention are preferably used in amounts of from 50% by weight to 80% by weight, in particular from 65% by weight to 75% by weight, in each case based on the total agent, in the production of cleaning or washing agents. In particular for the production of cleaning agents, it is possible for the remainder to consist of 100% by weight of abrasives. Additional, in particular nonionic, surfactant is present in such washing or cleaning agents, with the exclusion of any surfactant mixture according to the invention Contained amount, preferably in amounts not more than 5 wt .-%, in particular from 0.5 wt .-% to 2 wt .-%, each based on the total agent.
  • Suitable foam inhibitors include long-chain soaps, in particular beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 3436194, European patent applications EP 262588, EP 301414, EP 309931 or European patent EP 150386.
  • foam inhibitors based on the active substances mentioned, are preferably in amounts of not more than 1% by weight, in particular from 0.1% by weight to 1% by weight. , each based on the total agent and including the amount that may be contained in the surfactant mixture according to the invention.
  • the bleaching agents which can be considered as further constituents of such agents are the peroxygen compounds generally used in detergents, such as perborate, which can be present as a tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts in particular as sodium salts.
  • Such bleaches are contained in detergents or cleaning agents produced using surfactant mixtures according to the invention, preferably in amounts of not more than 25% by weight, in particular from 12% by weight to 20% by weight, in each case based on the total agent.
  • the component of the bleach activators comprises the commonly used N- or 0-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopamideazines, cyanuryl amide, sulfuryl also carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl phenol sulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose.
  • N- or 0-acyl compounds for example multiply acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated
  • the bleach activators can be coated or granulated with Hü11 substances in a known manner to avoid the interaction with the per-compounds during storage, with tetraacetylethylenediamine granulated with carboxymethyl cellulose with average grain sizes of 0.01 mm to 0.8 m, as described, for example, by The method described in the European patent EP 037026 can be produced, is particularly preferred.
  • Bleach activators of this type are preferably contained in amounts of not more than 10% by weight, in particular from 2% by weight to 8% by weight, in each case based on the total agent, in detergents or cleaning agents prepared using surfactant mixtures according to the invention.
  • Suitable enzymes are those from the class of proteases, lipases, amylases and cellulases and their mixtures, which are stable and active even under the temperature conditions of white washing. Enzymes obtained from fungi or bacterial strains such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus and Streptomyces griseus are preferably used. The enzymes used can be adsorbed onto carrier substances in a known manner, embedded in coating substances and / or granulated with the aid of carrier substances in order to make them easier to handle and to protect them against premature inactivation.
  • Such enzymes are preferably in amounts of not more than 2% by weight, in particular from 0.4% by weight to 1.2% by weight, in detergents or cleaning agents prepared using surfactant mixtures according to the invention, in each case based on the total mean.
  • the detergents and cleaning agents produced using the surfactant mixtures according to the invention are stable in storage, free-flowing and stable in color. Another advantage is that when the surfactant mixtures according to the invention are used, largely inert filler salts, in particular alkali metal sulfate, can be dispensed with. Examples
  • Alkyl sulfate, the sodium silicate and the alkyl glycoside, the zeolite in the form of an approximately 50% by weight aqueous slurry, the alkyl glycoside as an approximately 50% by weight aqueous solution and the sodium silicate in the form of an approximately 35% by weight water glass solution was set, an aqueous slurry containing 44 wt .-% water was generated from the raw materials listed in Table 1.
  • This slurry which had viscosities of 4500 mPa.s to 6400 mPa.s at 60 ° C to 80 ° C, was heated to temperatures of approximately 60 ° C to 80 ° C and
  • the free-flowing powder Ml characterized in Table 1 by its composition was obtained with an average grain size of around 0.5 mm, which was free of particles over 1.8 mm in diameter, had dust contents of 0.15% by weight and a bulk density of Had 540 grams per liter.
  • the detergent W1 was prepared by simply mixing the amount of the powder according to the invention specified in the table below with conventional detergent ingredients. In washing tests under application conditions (drum washing machine Miele W 716, 3.5 kg of normally soiled laundry, water hardness 16 ° d, dosage 98 g detergent), this showed an average of all soiling at 30 ° C as well as at 60 ° C and 90 ° C a washing power which at least reached the level of a commercial heavy-duty detergent tested for comparison purposes with a fatty alkyl polyethoxylate / alkylbenzenesulfonate surfactant component.
  • the agent according to the invention performed significantly better, especially in the case of cosmetic soiling.

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

Abstract

A process for preparing powdery surface-active agent mixtures by spray drying aqueous suspensions of the ingredients should allow the normally used alkylbenzol-sulphonate to be replaced by alkylsulphate, without causing the spontaneous inflammation of the spray-dried goods but allowing pourable and flowable, non-clotting powdery products to be obtained. For that purpose, an amount comprised between 2 and 15 parts by weight alkylsulphate having the formula R?1-OSO3?X, in which R?1 stands for an alkyl residue with 10 to 20 C atoms and X for an ammonium ion possibly substituted by alkali, ammonium, alkyl or hydroxyalkyl, an amount comprised between 1 and 5 parts by weight alkylglycoside having the formula R?2-O(G)n?, in which R?2 stands for an alkyl residue with 8 to 22 C atoms, G stands for a glycose unit and n is a number from 1 to 10, the weight ratio between alkylsulphate and alkylglycoside being comprised between 8:1 and 1:1, and an amount comprised between 20 and 100 parts by weight of an essentially anorganic, phosphate-free excipient containing alkali carbonate and alkali alumosilicate in a weight ratio comprised between 2:1 and 1:3, are mixed with enough water to produce a flowable and pumpable mixture, which is then spray-dried using drying gasses at temperatures below 250 C until so much water is removed that a powdery, pourable product is obtained.

Description

"Pulverförmiqe Tensidmischunq" "Powdery surfactant mixture"
Die Erfindung betrifft pulverförmige, schütt- und rieselfähige Tensid- mischungen, die Alkylsulfat, Alkylglykosid und anorganisches Trägermate¬ rial enthalten, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung als Vorgemische zur Herstellung von partikelför igen Wasch- und Reini¬ gungsmitteln.The invention relates to powdered, pourable and free-flowing surfactant mixtures which contain alkyl sulfate, alkyl glycoside and inorganic carrier material, a process for their preparation and their use as premixes for the production of particulate detergents and cleaners.
In der US-amerikanischen Patentschrift US 4536319 werden granuläre Waschmittel beschrieben, die 2 bis 30 Gew.-% bestimmter Alkylpolysaccha- ride, anionische Cotenside, wasserlösliche Salze und bis zu 55 Gew.-% Alumosilikat enthalten. Bevorzugte Aniontenside sind dort Alkylbenzol- sulfonate. Unter Einsatz von anderen Aniontensiden, insbesondere-iAlkyl- sulfaten, erhält man nach dem dort vorgeschlagenen Herstellungsverfahren durch Sprühtrocknung Pulverprodukte, die ein nicht vollständig befriedi¬ gendes Rieselvermögen aufweisen.US Pat. No. 4,536,319 describes granular detergents which contain 2 to 30% by weight of certain alkyl polysaccharides, anionic cosurfactants, water-soluble salts and up to 55% by weight of aluminosilicate. Preferred anionic surfactants there are alkylbenzenesulfonates. With the use of other anionic surfactants, in particular i-alkyl sulfates, spray drying gives powder products which do not have a completely satisfactory free-flowing capacity by spray drying.
Aus der internationalen Patentanmeldung WO 87/02053 ist ein Verfahren zur Herstellung teilchenförmiger Waschmittel durch Trocknen einer 40- bis 80- prozentigen wäßrigen Aufschlämmung bekannt, die, bezogen auf entstehenden Feststoff, 2 bis 60 Gew.-% Tenside, die zu mindestens 0,1 Gew.-% aus Al¬ kylglykosiden bestehen, wobei die Gesamtmenge an Alkylglykosiden höchstens 2 Gew.-% beträgt, 5 bis 70 Gew.-% Buildersubstanzen und bis zu 40 Gew.-% wasserlösliche Füllstoffe enthält. In derartigen Aufschlämmungen wirken die Alkylglykoside als Viskositätserniedriger. Bevorzugt eingesetzte Ten¬ side sind anionische Tenside, insbesondere solche vom Typ der Alkyl- benzolsulfonate, und nichtionische Tenside, insbesondere ethoxylierte Fettalkohole. Der Entzug des Wassers aus der Aufschlämmung wird vorzugs¬ weise durch Sprühtrocknen erreicht.From international patent application WO 87/02053 a process for the production of particulate detergents by drying a 40 to 80 percent aqueous slurry is known which, based on the resulting solid, contains 2 to 60% by weight of surfactants, which are at least 0.1 % By weight consist of alkyl glycosides, the total amount of alkyl glycosides being at most 2% by weight, containing 5 to 70% by weight builder substances and up to 40% by weight water-soluble fillers. In such slurries, the alkyl glycosides act as lower viscosity. Preferred surfactants are anionic surfactants, especially those of the alkylbenzenesulfonate type, and nonionic surfactants, especially ethoxylated fatty alcohols. The water is preferably removed from the slurry by spray drying.
Der Einsatz von Alkylbenzolsulfonat in Wasch- und Reinigungsmitteln wird in neuerer Zeit wegen der Erdöl-Basis dieses Tensids in Frage gestellt. Als umweltverträglichere Tenside mit vergleichbar guten Reinigungseigen¬ schaften kommen zum Beispiel Sulfatierungsprodukte von aus nachwachsenden Rohstoffen zugänglichen Verbindungen, insbesondere Fettalkoholen, in Be¬ tracht. Während allerdings alkylbenzolsulfonathaltige wäßrige Aufschläm¬ mungen problemlos bei den in derartigen Verfahren üblichen Temperaturen, normalerweise etwa 250 °C bis 350 °C, sprühgetrocknet werden können, be¬ steht bei wäßrigen Aufschlämmungen, welche vergleichbare Mengen an anderen Tensiden, insbesondere Alkylsulfaten enthalten, die Gefahr der Selbstent¬ zündung.The use of alkylbenzenesulfonate in detergents and cleaning agents has recently been called into question because of the petroleum base of this surfactant. For example, sulfation products of compounds accessible from renewable raw materials, in particular fatty alcohols, come into consideration as more environmentally compatible surfactants with comparable good cleaning properties. However, while aqueous slurries containing alkylbenzenesulfonate can be spray-dried without problems at the temperatures customary in such processes, normally about 250 ° C. to 350 ° C., there is a risk with aqueous slurries which contain comparable amounts of other surfactants, in particular alkyl sulfates self-ignition.
Es bestand daher die Aufgabe, ein Verfahren zu entwickeln, welches die Herstellung alkylbenzolsulfonatfreier pulverförmiger Tensidmischungen durch Sprühtrocknen einer wäßrigen tensidhaltigen Aufschlämmung erlaubt, ohne daß es bei der Herstellung zur Selbstentzündung des Sprühtrocknungs¬ produktes kommt, wobei die pulverförmigen Erzeugnisse schütt- und riesel¬ fähig sein sollen.The object was therefore to develop a process which allows the preparation of powdered surfactant mixtures free from alkylbenzenesulfonate by spray drying an aqueous surfactant-containing slurry, without the self-ignition of the spray drying product occurring during production, the powdered products being free-flowing and free-flowing should.
Diese Aufgabe wird durch das erfindungsgemäße Verfahren zur Herstellung pulverförmiger Tensidmischungen gelöst, das im wesentlichen darin besteht, daß man eine Menge von 2 bis 15 Gewichtsteilen Alkylsulfat der Forirel I,This object is achieved by the process according to the invention for the production of powdered surfactant mixtures, which essentially consists in that an amount of 2 to 15 parts by weight of alkyl sulfate of Forirel I,
in der R* einen Alkylrest mit 10 bis 20 C-Atomen und X ein Alkali-, Ammo¬ nium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituiertes Ammoniumion bedeuten, eine Menge von 1 bis 5 Gewichtsteilen Alkylglykosid der Formelin which R * is an alkyl radical having 10 to 20 C atoms and X is an alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion, an amount of 1 to 5 parts by weight of alkylglycoside of the formula
II.II.
R2-0(G)n (II)R 2 -0 (G) n (II)
in der R^ einen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und n eine Zahl von 1 bis 10 bedeuten, wobei das Gewichtsverhältnis von Alkylsulfat zu Alkylglykosid 8:1 bis 1:1, vorzugsweise 5:1 bis 2:1, be¬ trägt, und eine Menge von 20 bis 100 Gewichtsteilen eines im wesentlichen anorganischen phosphatfreien Trägermaterials, welches Alkalicarbonat und Alkalialumosilikat im Gewichtsverhältnis 2:1 bis 1:3 enthält, mit so viel Wasser mischt, daß eine bei Temperaturen unter 95 °C fließfähige und pumpbare Mischung mit einer Viskosität von 3000 mPa-s bis 15000 mPa-s, gemessen bei 60 °C bis 95 °C, entsteht, und dieser durch Sprühtrocknung unter Verwendung von Trocknungsgasen mit Temperaturen unter 250 °C das Wasser soweit entzieht, daß ein pulverförmiges, rieselfähiges Produkt entsteht. Dies ist in der Regel bei Wassergehalten im Pulverprodukt von nicht mehr als 20 Gew.-%, insbesondere von 5 Gew.-% bis 15 Gew.-% der Fall. In Formulierungen, in denen das Trägermaterial einen Teil des Was¬ sers als Kristallwasser bindet, bezieht sich der Rest-Wassergehalt auf das freie, nicht im Kristallgitter gebundene Wasser.in which R 1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10, the weight ratio of alkyl sulfate to alkyl glycoside being 8: 1 to 1: 1, preferably 5: 1 to 2: 1 , be¬, and an amount of 20 to 100 parts by weight of an essentially inorganic phosphate-free carrier material which contains alkali carbonate and alkali alumosilicate in a weight ratio of 2: 1 to 1: 3, with as much Water mixes that a flowable and pumpable mixture at temperatures below 95 ° C with a viscosity of 3000 mPa-s to 15000 mPa-s, measured at 60 ° C to 95 ° C, is formed, and this by spray drying using drying gases Temperatures below 250 ° C withdraw the water to such an extent that a powdery, free-flowing product is formed. This is usually the case when the water content in the powder product is not more than 20% by weight, in particular from 5% by weight to 15% by weight. In formulations in which the carrier material binds part of the water as crystal water, the residual water content relates to the free water not bound in the crystal lattice.
Vorzugsweise wird das Verfahren derart ausgeführt, daß man 3 bis 10 Ge¬ wichtsteile Alkylsulfat gemäß Formel I, 2 bis 3 Gewichtsteile Alkylgly¬ kosid gemäß Formel II und 25 bis 80 Gewichtsteile des anorganischen Trä¬ germaterials mit so viel Wasser mischt, daß eine mindestens 35 Gew.-%, insbesondere 40 Gew.-% bis 50 Gew.-% Wasser enthaltende Mischung entsteht.The process is preferably carried out in such a way that 3 to 10 parts by weight of alkyl sulfate according to formula I, 2 to 3 parts by weight of alkyl glycoside according to formula II and 25 to 80 parts by weight of the inorganic carrier material are mixed with so much water that at least 35 % By weight, in particular 40% by weight to 50% by weight of water, is formed.
Das phosphatfreie im wesentlichen anorganische Trägermaterial besteht vorzugsweise zu 40 Gew.-% bis 60 Gew.-% aus Alkalialumosilikat, insbeson¬ dere Zeolith NaA und/oder NaX, zu 20 Gew.-% bis 40 Gew.-% aus Alkalicar¬ bonat, bis zu 20 Gew.-% aus weiteren anorganischen Salzen, insbesondere Alkalisilikaten, Alkalihydrogencarbonaten und/oder Alkalichloriden, und zu nicht mehr als 20 Gew.-% aus organischem Material, insbesondere Alkali- polycarboxylat. Die genannten weiteren anorganischen Salze sind in dem Trägermaterial insbesondere in Mengen von 1 Gew.-% bis 10 Gew.-% enthal¬ ten, wobei das Trägermaterial frei von Alkalisilikat mit einem Molver¬ hältnis Siθ2 zu Alkalioxid bis zu 2 ist und der Anteil an Alkalisilikat mit einem Molverhältnis Siθ2 zu Alkalioxid über 2 nicht mehr als 5 Gew.-%, jeweils bezogen auf gesamtes Trägermaterial, beträgt. Das Trägermaterial ist vorzugweise ebenfalls frei von Alkalisulfaten. Im Rahmen der Erfindung geeignete Alumosilikate weisen keine Teilchen mit einer Korngröße über 30 μm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 μm. Ihr Calciumbindevermögen, das nach den An¬ gaben der deutschen Patentschrift DE 24 12837 bestimmt werden kann, liegt im Bereich von 100 bis 200 mg CaO pro Gramm. Bei den erwähnten Polycarboxylaten handelt es sich um bekannte Cobuildersubstanzen in Form polymerer Polycarbonsäuren beziehungsweise deren wasserlöslicher Salze, insbesondere Alkalisalze, welche durch Polymerisation von Acrylsäure-, Methacrylsäure- und/oder Maleinsäure-Monomeren beziehungsweise deren Salzen erhältlich sind. Derartige Substanzen sind in dem Trägermaterial vorzugsweise in Mengen von 1 Gew.-% bis 15 Gew.-%, insbesondere von 5 Gew.-% bis 13 Gew.-%, jeweils bezogen auf gesamtes Trägermaterial, ent¬ halten. Bevorzugtes Alkalimetall ist bei allen genannten Inhaltsstoffen Natrium.The phosphate-free, essentially inorganic carrier material preferably consists of 40% by weight to 60% by weight of alkali alumosilicate, in particular zeolite NaA and / or NaX, 20% by weight to 40% by weight of alkali carbonate, up to 20% by weight of other inorganic salts, in particular alkali silicates, alkali hydrogen carbonates and / or alkali chlorides, and not more than 20% by weight of organic material, in particular alkali polycarboxylate. The further inorganic salts mentioned are contained in the carrier material in particular in amounts of 1% by weight to 10% by weight, the carrier material being free from alkali silicate with a molar ratio of SiO 2 to alkali oxide up to 2 and the proportion of Alkali silicate with a molar ratio of SiO 2 to alkali oxide over 2 is not more than 5% by weight, in each case based on the total support material. The carrier material is preferably also free of alkali sulfates. Alumosilicates suitable in the context of the invention have no particles with a grain size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12837, is in the range from 100 to 200 mg CaO per gram. The polycarboxylates mentioned are known cobuilder substances in the form polymeric polycarboxylic acids or their water-soluble salts, in particular alkali salts, which can be obtained by polymerizing acrylic acid, methacrylic acid and / or maleic acid monomers or their salts. Such substances are preferably contained in the carrier material in amounts of from 1% by weight to 15% by weight, in particular from 5% by weight to 13% by weight, based in each case on the entire carrier material. The preferred alkali metal for all of the ingredients mentioned is sodium.
Die Sprühtrocknung der wäßrigen Aufschlämmungen erfolgt in üblicherweise dafür vorgesehenen Anlagen, sogenannten Sprühtürmen, in deren oberem Teil die Aufschlämmung durch Druckdüsen zu feinen Tröpfchen versprüht wird, die sich unter Einwirkung der Schwerkraft in den unteren Teil des Sprühturms bewegen und dabei mit heißen Trocknungsgasen in Kontakt kommen, die im Gleichstrom oder vorzugsweise im Gegenstrom zu den zu trocknenden Parti¬ keln geführt werden. Dabei ist darauf zu achten, daß die Temperatur der Trocknungsgase nicht so hoch liegt, daß die Temperatur der sprühgetrock¬ neten Partikel über die Selbstentzündungstemperatur dieser Partikel steigt. Im Rahmen der Erfindung bedeutet dies, daß die Temperatur der Trocknungsgase einen Wert von 250 °C nicht überschreitet und vorzugsweise im Bereich von 120 °C bis 240 °C, insbesondere von 140 °C bis 210 °C liegt, wobei die Trocknungsgastemperatur an "der heißesten Stelle des Trockenturms, dem sogenannten Ringkanal, gemessen wird.The spray-drying of the aqueous slurries takes place in systems usually provided for this purpose, so-called spray towers, in the upper part of which the slurry is sprayed into fine droplets by pressure nozzles, which move under the action of gravity into the lower part of the spray tower and come into contact with hot drying gases which are guided in cocurrent or preferably in countercurrent to the particles to be dried. It is important to ensure that the temperature of the drying gases is not so high that the temperature of the spray-dried particles rises above the self-ignition temperature of these particles. In the present invention this means that the temperature of the drying gas does not exceed a value of 250 ° C and preferably in the range of 120 ° C to 240 ° C, in particular from 140 ° C to 210 ° C, wherein the drying gas temperature at "the hottest point of the drying tower, the so-called ring channel, is measured.
Bei der Zubereitung der zu den erfindungsgemäßen Mischungen führenden Aufschlämmungen ist die Einarbeitung wäßriger, in der Regel 30- bis 60- gewichtsprozentiger Alkylglykosid-Pasten, wie sie im Rahmen der Alkylgly- kosid-HersteTlung und gegebenenfalls anschließendem Bleichen üblicherweise anfallen, möglich. Ebenso kann die Alkylsulfat-Komponente und insbesondere die Träger-Komponente als wäßrige Lösung oder Aufschlämmung eingesetzt werden. Um die leichte Fließ- und Pumpfähigkeit der zu versprühenden Auf¬ schlämmung bei Temperaturen unter 95 °C, insbesondere 60 °C bis 80 °C, zu gewährleisten, hat es sich als vorteilhaft erwiesen, wenn mindestens etwa 35 Gew.-%, vorzugsweise 40 bis 50 Gew.-% Wasser in der zu trocknenden Aufschlämmung vorhanden ist. Dabei ist als weiterer Vorteil des erfin- ' dungsgemäßen Verfahrens die mit Werten im Bereich von 3000 mPa*s bis 15000 mPa'S bei Temperaturen in dem genannten Bereich überraschend nied¬ rige Viskosität der zu den erfindungsgemäßen pulverförmigen Tensidmischungen führenden Aufschlämmungen gegenüber Aufschlämmungen, die statt Alkylsulfat die gleiche Menge Alkylbenzolsulfonat enthalten, zu werten.In the preparation of the slurries leading to the mixtures according to the invention, it is possible to incorporate aqueous, generally 30 to 60% by weight alkyl glycoside pastes, as are usually obtained in the context of alkyl glycoside production and, if appropriate, subsequent bleaching. Likewise, the alkyl sulfate component and in particular the carrier component can be used as an aqueous solution or slurry. In order to ensure the easy flow and pumpability of the slurry to be sprayed at temperatures below 95 ° C., in particular 60 ° C. to 80 ° C., it has proven to be advantageous if at least about 35% by weight, preferably 40 up to 50% by weight of water is present in the slurry to be dried. It is a further advantage of the inventions' to the invention process with values ranging from 3000 mPa * s up 15000 mPa'S at temperatures in the range mentioned, surprisingly low viscosity of the slurries leading to the powdered surfactant mixtures according to the invention compared to slurries which contain the same amount of alkylbenzenesulfonate instead of alkyl sulfate.
Die durch das erfindungsgemäße Verfahren hergestellten erfindungsgemäßen pulverförmigen, schütt- und rieselfähigen Tensidmischungen enthalten vor¬ zugsweise 10 Gew.-% bis 30 Gew.-% Alkylsulfat der Formel I,The powdery, pourable and free-flowing surfactant mixtures according to the invention produced by the process according to the invention preferably contain 10% by weight to 30% by weight of alkyl sulfate of the formula I,
R!-0S03X (I)R! -0S03X (I)
in der R* einen Alkylrest mit 10 bis 20 C-Atomen und X ein Alkali-, Ammo¬ nium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituiertes Ammoniumion bedeuten, 2 Gew.-% bis 10 Gew.-% Alkylglykosid der Formel II,in which R * is an alkyl radical having 10 to 20 carbon atoms and X is an alkali metal, ammonium or alkyl- or hydroxyalkyl-substituted ammonium ion, 2% by weight to 10% by weight of alkyl glycoside of the formula II,
R2-0(G)n (II)R 2 -0 (G) n (II)
in der R2 einen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und n eine Zahl von 1 bis 10 bedeuten, wobei das Gewichtsverhältnis vonin which R2 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10, the weight ratio of
Alkylsulfat zu Alkylglykosid 8:1 bis 1:1 beträgt,Alkyl sulfate to alkyl glycoside is 8: 1 to 1: 1,
45 Gew.-% bis 70 Gew.-% eines im wesentlichen anorganischen Trägermateri- als, welches Alkalicarbonat und Alkalialumosilikat im Gewichtsverhältnis45% by weight to 70% by weight of an essentially inorganic carrier material, which contains alkali carbonate and alkali alumosilicate in a weight ratio
2:1 bis 1:3 enthält, und bis zu 20 Gew.-% Wasser.Contains 2: 1 to 1: 3, and up to 20 wt .-% water.
Als für den Einsatz in den erfindungsgemäßen alkylbenzolsulfonatfreien Tensidmischungen geeignete Alkylsulfate kommen die Verbindungen der Formel I, in der R* einen Alkylrest mit 10 bis 20 C-Atomen und X ein Alkali-, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituiertes Ammoniumion bedeuten, in Frage. Besonders geeignet sind die Derivate der Fettalkohole mit insbesondere 12 bis 18 C-Atomen und deren verzweigt- kettiger Analogen, der sogenannten Oxoalkohole. Die Alkylsulfate können in bekannter Weise durch Reaktion der entsprechenden Alkoholkomponente mit einem üblichen Sulfatierungsreagenz, insbesondere Schwefeltrioxid oder Chlorsulfonsäure, und anschließende Neutralisation mit Alkali-, Ammonium¬ oder Alkyl- beziehungsweise Hydroxyalkyl-substituierten Ammoniumbasen hergestellt werden. Derartige Alkylsulfate sind in den erfinduπgsgemäßen Pulvern vorzugsweise in Mengen von 10 Gew.-% bis 30 Gew.-%, insbesondere von 12 Gew.-% bis 25 Gew.-% enthalten.Suitable alkyl sulfates for use in the alkylbenzenesulfonate-free surfactant mixtures according to the invention are the compounds of the formula I in which R * is an alkyl radical having 10 to 20 C atoms and X is an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion Question. The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are particularly suitable. The alkyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or Chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Such alkyl sulfates are contained in the powders according to the invention preferably in amounts of 10% by weight to 30% by weight, in particular 12% by weight to 25% by weight.
Die zur Einarbeitung in die erfindungsgemäßen Tensidmischungen geeigneten Alkylglykoside sind Verbindungen der allgemeinen Formel II, in der R^ ei¬ nen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und n eine Zahl zwischen 1 und 10 bedeuten. Derartige Alkylglykoside und ihre Herstellung werden zum Beispiel in den europäischen Patentanmeldungen EP 92355, EP 301 298, EP 357 969 und EP 362 671 oder der US-amerikanischen Patent¬ schrift US 3547828 beschrieben. Bei der Glykosidkomponente ((G)n in Formel II) derartiger Alkylglykoside handelt es sich um Oligo- oder Poly¬ mere aus natürlich vorkommenden Aldose- oder Ketose-Monomeren, zu denen insbesondere Glucose, Mannose, Fruktose, Galaktose, Talose, Gulose, Alt¬ rose, Allose, Idose, Ribose, Arabinose, Xylose und Lyxose gehören. Die aus derartigen glykosidisch verknüpften Monomeren bestehenden Oligomere werden außer durch die Art der in ihnen enthaltenen Zucker durch deren Anzahl, den sogenannten Oligomerisierungsgrad, charakterisiert. Der Oligomeri- sierungsgrad (n in Formel II) nimmt als analytisch zu ermittelnde Größe im allgemeinen gebrochene Zahlenwerte an; er liegt bei Werten zwischen 1 und 10, bei den vorzugsweise eingesetzten Alkylglykosiden unter einem Wert von 1,5, insbesondere zwischen 1,2 und 1,4. Bevorzugter Monomer-Baustein ist wegen der guten Verfügbarkeit Glucose.The alkyl glycosides suitable for incorporation into the surfactant mixtures according to the invention are compounds of the general formula II in which R 1 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10. Such alkyl glycosides and their preparation are described, for example, in European patent applications EP 92355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3547828. The glycoside component ((G) n in formula II) of such alkyl glycosides are oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, alt ¬ rose, allose, idose, ribose, arabinose, xylose and lyxose belong. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of oligomerization (n in formula II) generally assumes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the alkyl glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability.
Der Alkylteil (R2 in Formel II) der in den erfindungsgemäßen Tensidmi¬ schungen enthaltenen Alkylglykoside stammt bevorzugt ebenfalls aus leicht zugänglichen Derivaten nachwachsender Rohstoffe, insbesondere aus Fettal¬ koholen, obwohl auch deren verzweigtkettige Isomere, insbesondere soge¬ nannte Oxoalkohole, zur Herstellung verwendbarer Alkylglykoside eingesetzt werden können. Brauchbar sind demgemäß insbesondere die primären Alkohole mit linearen Octyl-, Decyl-, Dodecyl-, Tetradecyl-, Hexadecyl- oder Octa- decylresten sowie deren Gemische. Besonders geeignete Alkylglykoside enthalten einen Kokosfettalkylrest, das heißt Mischungen mit im wesent¬ lichen Rl=Dodecyl und R*=Tetradecyl. Die Alkylglykoside können herstel- lungsbedingt geringe Mengen, beispielsweise 1 bis 2 %, an nicht umge¬ setztem freiem Fettalkohol enthalten, was sich nicht nachteilig auf die Eigenschaften der damit hergestellten Pulverprodukte auswirkt.The alkyl part (R 2 in formula II) of the alkyl glycosides contained in the surfactant mixtures according to the invention preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, are also suitable for the production of alkyl glycosides can be used. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octa-decyl radicals and mixtures thereof are particularly useful. Particularly suitable alkyl glycosides contain a coconut fatty alkyl radical, that is to say mixtures with essentially Rl = dodecyl and R * = tetradecyl. The alkyl glycosides can be contain small amounts, for example 1 to 2%, of unreacted free fatty alcohol, which does not have a disadvantageous effect on the properties of the powder products produced therewith.
Derartige Alkylglykoside sind in den erfindungsgemäßen Tensidmischungen in Mengen von 2 Gew.-% bis 10 Gew.-%, vorzugsweise von 3 Gew.-% bis 8 Gew.-% enthalten, wobei das Gewichtsverhältnis von Alkylsulfat zu Alkylglykosid 8:1 bis 1:1, vorzugsweise 5:1 bis 2:1 beträgt.Such alkyl glycosides are contained in the surfactant mixtures according to the invention in amounts of 2% by weight to 10% by weight, preferably 3% by weight to 8% by weight, the weight ratio of alkyl sulfate to alkyl glycoside being 8: 1 to 1: 1, preferably 5: 1 to 2: 1.
Darüberhinaus können die erfindungsgemäßen Gemische weitere Tenside, vor¬ zugsweise nichtionische Tenside und/oder Aniontenside und unter diesen insbesondere Fettsäureseifen mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen, und Tenside des Sulfat- oder Sulfonat-Typs, in Mengen von vor¬ zugsweise nicht über 5 Gew.-%, insbesondere von 0,1 Gew.-% bis 3 Gew.-%, jeweils bezogen auf gesamte Tensidzubereitung, enthalten. Zu den zusätz¬ lich brauchbaren Tensiden vom Sulfat-Typ gehören die sulfatierten Alkoxy- lierungsprodukte der genannten Alkohole, sogenannte Ethersulfate. Vor¬ zugsweise enthalten derartige Ethersulfate 2 bis 30, insbesondere 4 bis 10, Ethylenglykol-Gruppen pro Molekül. Zu den geeigneten Aniontensiden gehören auch die durch Umsetzung von Fettsäureestern mit Schwefeltrioxid und anschließender Neutralisation erhältlichen oc-Sulfoester, insbesondere die sich von Fettsäuren mit 8 bis 22 C-Atomen, vorzugsweise 12 bis 18 C- Atomen, und linearen Alkoholen mit 1 bis 6 C-Atomen, vorzugsweise 1 bis 4 C-Atomen, ableitenden Sulfonierungsprodukte.In addition, the mixtures according to the invention can contain other surfactants, preferably nonionic surfactants and / or anionic surfactants and, in particular, fatty acid soaps with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and surfactants of the sulfate or sulfonate type preferably not more than 5% by weight, in particular from 0.1% by weight to 3% by weight, based in each case on the total surfactant preparation. The sulphated alkoxylation products of the alcohols mentioned, so-called ether sulphates, belong to the additionally usable surfactants of the sulphate type. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants also include the oc-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms -Atoms, preferably 1 to 4 carbon atoms, derived sulfonation products.
Zu den in Frage kommenden nichtionischen Tensiden gehören die Alkoxylate, insbesondere die Ethoxylate und/oder Propoxylate von linearen oder ver- zweigtkettigen Alkoholen mit 10 bis 22 C-Atomen, vorzugsweise 12 bis 18 C-Atomen. Der Alkoxylierungsgrad der Alkohole liegt dabei zwischen 1 und 20, vorzugsweise zwischen 3 und 10. Sie können in bekannter Weise durch Umsetzung der entsprechenden Alkohole mit den entsprechenden Alkylenoxiden hergestellt werden. Geeignet sind insbesondere die Derivate der Fettalko¬ hole, obwohl auch deren verzweigtkettige Isomere, insbesondere sogenannte Oxoalkohole, zur Herstellung verwendbarer Alkoxylate eingesetzt werden können. Brauchbar sind demgemäß insbesondere die Ethoxylate primärer Al¬ kohole mit linearen Dodecyl-, Tetradecyl-, Hexadecyl- oder Octadecylresten sowie deren Gemische. Außerdem sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylaminen, vicinalen Diolen und Carbon- säureamiden, die hinsichtlich des Alkylteils den genannten Alkoholen ent¬ sprechen, verwendbar.The nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the ethoxylates of primary alcohols with linear dodecyl, tetradecyl, hexadecyl or octadecyl radicals are particularly useful as well as their mixtures. Corresponding ethoxylation and / or propoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl moiety can also be used.
Zusätzlich können die erfindungsgemäßen Zubereitungen in geringen Mengen, vorzugsweise insgesamt nicht über 5 Gew.-%, weitere in Wasch- und Reini¬ gungsmitteln übliche Bestandteile enthalten, die unter den Sprühtrock¬ nungsbedingungen stabil sind. Zu diesen fakultativen Bestandteilen gehören insbesondere Komplexbi iner für Schwermetalle, beispielsweise Aminopoly- carbonsäuren, Aminohydroxypolycarbonsäuren, Polyphosphonsäuren und/oder Aminopolyphosphonsäuren, Vergrauungsinhibitoren, beispielsweise Celluloseether, Schauminhibitoren, beispielsweise Organopolysiloxane oder Paraffine, und optische Aufheller, beispielsweise Stilbendisulfonsäurede- rivate. Vorzugsweise sind in den erfiπduπgsgemäßen Tensidmischungen nicht über 1 Gew.-%, insbesondere 0,01 Gew.-% bis 0,5 Gew.-% optische Aufheller, insbesondere Verbindungen aus der Klasse der substituierten 4,4'-Bis- (2,4,6-triamino-s-triazinyl)-stilben-2,2'-disulfonsäuren, nicht über 5 Gew.-%, insbesondere 0,1 Gew.-% bis 2 Gew.-% Komplexbildner für Schwer- metalle, insbesondere Aminoalkylenphosphonsäuren und deren Salze, nicht über 3 Gew.- , insbesondere 0,5 Gew.-% bis 2 Gew.-% Vergrauungsinhibitoren und nicht über 2 Gew.-%, insbesondere 0,1 Gew.-% bis 1 Gew.-% Schauminhi¬ bitoren enthalten, wobei sich die genannten Gewichtsanteile auf die ge¬ samte Tensidmischung beziehen.In addition, the preparations according to the invention can contain small amounts, preferably not more than 5% by weight in total, of further constituents which are customary in washing and cleaning agents and are stable under the spray drying conditions. These optional constituents include, in particular, complex biiners for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, graying inhibitors, for example cellulose ethers, foam inhibitors, for example organopolysiloxanes or paraffins, and optical brighteners, for example stilbene derivative disulphons. Preferably, the inventive surfactant mixtures do not contain more than 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4'-bis (2, 4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, not more than 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, not more than 3% by weight, in particular 0.5% by weight to 2% by weight, of graying inhibitors and not more than 2% by weight, in particular 0.1% by weight to 1% by weight, of foam inhibitor Contain bitters, the weight percentages referring to the entire surfactant mixture.
Die erfindungsgemäßen pulverförmigen Tensidmischungen werden insbesondere als schütt- und rieselfähiges Vorprodukte für die Herstellung von parti- kelförmigen Wasch- oder Reinigungsmitteln verwendet.The powdered surfactant mixtures according to the invention are used in particular as pourable and free-flowing precursors for the production of particulate detergents or cleaning agents.
Zur Verwendung als Vorgemische für die Herstellung pulverförmiger Wasch- und Reinigungsmittel sollten die erfindungsgemäßen Pulver mittlere Korn¬ größen von vorzugsweise 0,2 mm bis 0,4 mm aufweisen und weitgehend frei von Teilchen mit Durchmessern über 2 mm oder unter 50 μm sein. Diese Grenzen werden von den durch Sprühtrocknen erhaltenen Tensidmischungen normalerweise eingehalten, ansonsten können Partikel außerhalb dieses Größenbereichs durch einfaches Aussieben entfernt und in den Herstel- lungsprozeß zurückgeführt werden. Vorzugsweise liegt die Schüttdichte der erfindungsgemäßen Pulverprodukte zwischen 400 und 600 Gramm pro Liter. Gewünschtenfalls kann ihr Litergewicht durch im Prinzip übliches Nachver¬ dichten erhöht werden, falls sie zur Herstellung von Wasch- oder Reini¬ gungsmitteln mit hohem Litergewicht, sogenannten Schwerpulvern, verwendet werden sollen.For use as premixes for the production of powdered detergents and cleaning agents, the powders according to the invention should have average grain sizes of preferably 0.2 mm to 0.4 mm and should be largely free of particles with diameters of more than 2 mm or less than 50 μm. These limits are normally met by the surfactant mixtures obtained by spray drying, otherwise particles outside this size range can be removed by simple sieving and used in the manufacturing process. development process. The bulk density of the powder products according to the invention is preferably between 400 and 600 grams per liter. If desired, their liter weight can be increased in principle by conventional densification, if they are to be used for the production of detergents or cleaning agents with a high liter weight, so-called heavy powders.
Die erfindungsgemäßen Zubereitung sind rieselfähige, freifließende Pulver, die ihre vorteilhaften Eigenschaften auch bei längerer Lagerung nicht verlieren. Sie sind auch aufhellerfrei hellfarbig, von akzeptablem Geruch und zeigen keine Neigung zum Verklu pen. Im Gegensatz dazu wurde bei Pul¬ vern, die statt Alkylsulfat gleiche Mengen an Alkylbenzolsulfonat ent¬ hielten, starkes Verklumpen festgestellt. Derartige Produkte waren über¬ dies unakzeptabel braun gefärbt, auch wenn nur relativ geringe Mengen Alkylglykosid, beispielsweise 3 Gew.-% oder darunter, in ihnen enthalten war. Um so mehr überraschen die unerwartet positiven Eigenschaften der erfindungsgemäßen Tensidmischungen.The preparations according to the invention are free-flowing, free-flowing powders which do not lose their advantageous properties even after prolonged storage. They are also lightening-free, light-colored, have an acceptable odor and show no tendency to jam. In contrast, strong clumping was found in powders which contained the same amounts of alkylbenzenesulfonate instead of alkyl sulfate. Products of this type were also unacceptably colored brown, even if they contained only relatively small amounts of alkyl glycoside, for example 3% by weight or less. All the more surprising are the unexpectedly positive properties of the surfactant mixtures according to the invention.
Zur Herstellung von Reinigungs- oder Waschmitteln können die erfindungs¬ gemäßen Tensidmischungen in im Prinzip bekannter Weise mit sonstigen in derartigen Mitteln üblichen pulverförmigen oder pulverförmig konfektio¬ nierbaren Bestandteilen vermischt werden, zu denen insbesondere Bleich¬ mittel, Bleichaktivatoren, Enzyme, Schauminhibitoren, optische Aufheller, Vergrauungsinhibitoren, beispielsweise Celluloseether und Abrasivstoffe, beispielsweise Quarzmehl, gehören. Auch das Aufsprühen von flüssigen, verflüssigten oder gelösten Inhaltsstoffen, beispielsweise Flüssigenzymen, Farbstoffen, Duftstoffen oder weiteren Tensiden, insbesondere nichtio¬ nischen Tensiden, auf die erfindungsgemäßen Pulver ist in im Prinzip be¬ kannter Weise möglich. Vorzugsweise werden die erfindungsgemäßen Tensidmischungen in Mengen von 50 Gew.-% bis 80 Gew.-%, insbesondere von 65 Gew.-% bis 75 Gew.-%, jeweils bezogen auf gesamtes Mittel, bei der Herstellung von Reinigungs- oder Waschmitteln verwendet. Insbesondere zur Herstellung von Reinigungsmitteln ist es möglich, daß der Rest auf 100 Gew.-% aus Abrasivstoffen besteht. Zusätzliches, insbesondere nichtionisches Tensid, ist in derartigen Wasch- oder Reinigungsmitteln, unter Ausschluß der eventuell in der erfindungsgemäßen Tensidmischung enthaltenen Menge, vorzugsweise in Mengen nicht über 5 Gew.-% insbeson¬ dere von 0,5 Gew.-% bis 2 Gew.-%, jeweils bezogen auf gesamtes Mittel, enthalten.To produce cleaning agents or detergents, the surfactant mixtures according to the invention can be mixed in a manner known in principle with other constituents in the form of powder or powder which are customary in such agents, in particular bleaching agents, bleach activators, enzymes, foam inhibitors, optical brighteners, Graying inhibitors, for example cellulose ethers and abrasives, for example quartz powder, belong. The spraying of liquid, liquefied or dissolved ingredients, for example liquid enzymes, dyes, fragrances or other surfactants, in particular nonionic surfactants, onto the powders according to the invention is also possible in a known manner. The surfactant mixtures according to the invention are preferably used in amounts of from 50% by weight to 80% by weight, in particular from 65% by weight to 75% by weight, in each case based on the total agent, in the production of cleaning or washing agents. In particular for the production of cleaning agents, it is possible for the remainder to consist of 100% by weight of abrasives. Additional, in particular nonionic, surfactant is present in such washing or cleaning agents, with the exclusion of any surfactant mixture according to the invention Contained amount, preferably in amounts not more than 5 wt .-%, in particular from 0.5 wt .-% to 2 wt .-%, each based on the total agent.
Zu den geeigneten Schauminhibitoren gehören langkettige Seifen, insbeson¬ dere Behenseife, Fettsäureamide, Paraffine, Wachse, Mikrokristallinwachse, Organopolysiloxane und deren Gemische, die darüberhinaus mikrofeine, ge¬ gebenenfalls silanierte oder anderweitig hydrophobierte Kieselsäure ent¬ halten können. Derartige Schauminhibitoren sind vorzugsweise an granuläre, wasserlösliche Trägersubstaπzen gebunden, wie beispielsweise in der deutschen Offenlegungsschrift DE 3436194, den europäischen Patentanmel¬ dungen EP 262588, EP 301414, EP 309931 oder der europäischen Patent¬ schrift EP 150386 beschrieben. In unter Verwendung erfindungsgemäßer Tensidmischungen hergestellten Wasch- oder Reinigungsmitteln sind derar¬ tige Schauminhibitoren, bezogen auf die genannten Aktivsubstanzen, vor¬ zugsweise in Mengen nicht über 1 Gew.-%, insbesondere von 0,1 Gew.-% bis 1 Gew.-%, jeweils bezogen auf gesamtes Mittel und unter Einschluß der eventuell in der erfindungsgemäßen Tensidmischung enthaltenen Menge, ent¬ halten.Suitable foam inhibitors include long-chain soaps, in particular beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobized silica. Such foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 3436194, European patent applications EP 262588, EP 301414, EP 309931 or European patent EP 150386. In detergents or cleaning agents produced using surfactant mixtures according to the invention, such foam inhibitors, based on the active substances mentioned, are preferably in amounts of not more than 1% by weight, in particular from 0.1% by weight to 1% by weight. , each based on the total agent and including the amount that may be contained in the surfactant mixture according to the invention.
Die als weitere Bestandteile derartiger Mittel in Betracht kommenden Bleichmittel sind die in Waschmitteln in der Regel verwendeten Perverbin¬ dungen wie Perborat, das als Tetra- oder Monohydrat vorliegen kann, Per- carbonat, Perpyrophosphat und Persilikat, die in der Regel als Alkalisal¬ ze, insbesondere als Natriumsalze, vorliegen. Derartige Bleichmittel sind in unter Verwendung erfindungsgemäßer Tensidmischungen hergestellten Wasch- oder Reinigungsmitteln vorzugsweise in Mengen nicht über 25 Gew.-%, insbesondere von 12 Gew.-% bis 20 Gew.-%, jeweils bezogen auf gesamtes Mittel, enthalten.The bleaching agents which can be considered as further constituents of such agents are the peroxygen compounds generally used in detergents, such as perborate, which can be present as a tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts in particular as sodium salts. Such bleaches are contained in detergents or cleaning agents produced using surfactant mixtures according to the invention, preferably in amounts of not more than 25% by weight, in particular from 12% by weight to 20% by weight, in each case based on the total agent.
Die Komponente der Bleichaktivatoren umfaßt die üblicherweise verwendeten N- oder 0-AcylVerbindungen, beispielsweise mehrfach acylierte Alkylendi- amine, insbesondere Tetraacetylethylendiaπrin, acylierte Glykolurile, ins¬ besondere Tetraacetylglykoluril, N-acylierte Hydantoine, Hydrazide, Triazole, Urazole, Diketopiperazine, Sulfurylamide und Cyanurate, außerdem Carbonsäureanhydride, insbesonder Phthalsäureanhydrid, Carbonsäureester, insbesondere Natrium-isononanoyl-phenolsulfonat, und acylierte Zuckerde¬ rivate, insbesondere Pentaacetylglukose. Die Bleichaktivatoren können zur Vermeidung der Wechselwirkung mit den Perverbindungen bei der Lagerung in bekannter Weise mit Hü11Substanzen überzogen beziehungsweise granuliert worden sein, wobei mit Hilfe von Carboxymethylcellulose granuliertes Tetraacetylethylendiamin mit mittleren Korngrößen von 0,01 mm bis 0,8 m, wie es beispielsweise nach dem in der europäischen Patentschrift EP 037026 beschriebenen Verfahren hergestellt werden kann, besonders be¬ vorzugt ist. In unter Verwendung erfindungsgemäßer Tensidmischungen her¬ gestellten Wasch- oder Reinigungsmitteln sind derartige Bleichaktivatoren vorzugsweise in Mengen nicht über 10 Gew.-%, insbesondere von 2 Gew.-% bis 8 Gew.-%, jeweils bezogen auf gesamtes Mittel, enthalten.The component of the bleach activators comprises the commonly used N- or 0-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylene diamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopamideazines, cyanuryl amide, sulfuryl also carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl phenol sulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose. The bleach activators can be coated or granulated with Hü11 substances in a known manner to avoid the interaction with the per-compounds during storage, with tetraacetylethylenediamine granulated with carboxymethyl cellulose with average grain sizes of 0.01 mm to 0.8 m, as described, for example, by The method described in the European patent EP 037026 can be produced, is particularly preferred. Bleach activators of this type are preferably contained in amounts of not more than 10% by weight, in particular from 2% by weight to 8% by weight, in each case based on the total agent, in detergents or cleaning agents prepared using surfactant mixtures according to the invention.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen und Cellulasen sowie deren Gemische in Frage, die auch bei den Tempera¬ turbedingungen der Weißwäsche stabil und aktiv sind. Vorzugsweise werden aus Pilzen oder Bakterienstämmen, wie Bacillus subtilis, Bacillus licheniformis, Bacillus lentus und Streptomyces griseus gewonnene enzyma- tische Wirkstoffe eingesetzt. Die verwendeten Enzyme können in bekannter Weise an Trägerstoffen adsorbiert, in Hüllsubstanzen eingebettet und/oder mit Hilfe von Trägersubstanzen granuliert worden sein, um sie leichter handhabbar zu machen und gegen vorzeitige Inaktivierung zu schützen. Der¬ artige Enzyme, insbesondere Proteasen, sind in unter Verwendung erfindungsgemäßer Tensidmischungen hergestellten Wasch- oder Reinigungs¬ mitteln vorzugsweise in Mengen nicht über 2 Gew.-%, insbesondere von 0,4 Gew.-% bis 1,2 Gew.-%, jeweils bezogen auf gesamtes Mittel, enthalten.Suitable enzymes are those from the class of proteases, lipases, amylases and cellulases and their mixtures, which are stable and active even under the temperature conditions of white washing. Enzymes obtained from fungi or bacterial strains such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus and Streptomyces griseus are preferably used. The enzymes used can be adsorbed onto carrier substances in a known manner, embedded in coating substances and / or granulated with the aid of carrier substances in order to make them easier to handle and to protect them against premature inactivation. Such enzymes, in particular proteases, are preferably in amounts of not more than 2% by weight, in particular from 0.4% by weight to 1.2% by weight, in detergents or cleaning agents prepared using surfactant mixtures according to the invention, in each case based on the total mean.
Die unter Verwendung der erfindungsgemäßen Tensidmischungen hergestellten Wasch- und Reinigungsmittel sind lagerstabil, rieselfähig und farbstabil. Als weiterer Vorteil ist zu werten, daß bei Einsatz der erfindungsgemäßen Tensidmischungen auf das Zumischen weitgehend inerter Füllsalze, insbe¬ sondere Alkalisulfat, verzichtet werden kann. BeispieleThe detergents and cleaning agents produced using the surfactant mixtures according to the invention are stable in storage, free-flowing and stable in color. Another advantage is that when the surfactant mixtures according to the invention are used, largely inert filler salts, in particular alkali metal sulfate, can be dispensed with. Examples
Beispiel 1example 1
Durch Zusammenmischen von Wasser, Na-Polycarboxylat, Zeolith und der Hälfte der Gesamtmenge des AlkylSulfates, Zugabe des Natriumcarbonats und anschließendes Vermischen mit einer Mischung aus dem restlichenBy mixing water, Na polycarboxylate, zeolite and half of the total amount of the alkyl sulfate together, adding the sodium carbonate and then mixing it with a mixture of the rest
Alkylsulfat, dem Natriumsilikat und dem Alkylglykosid, wobei der Zeolith in Form einer ca. 50-gewichtsprozentigen wäßrigen Aufschlämmung, das Alkylglykosid als ca. 50-gewichtsprozentige wäßrige Lösung und das Natri¬ umsilikat in Form einer ca. 35-gewichtsprozentigen Wasserglas-Lösung ein¬ gesetzt wurde, wurde aus den in Tabelle 1 angegebenen Rohstoffen eine wäßrige Aufschlämmung erzeugt, die 44 Gew.-% Wasser enthielt. Dieser Slurry, der bei 60 °C bis 80 °C Viskositäten von 4500 mPa.s bis 6400 mPa.s aufwies, wurden auf Temperaturen von etwa 60 °C bis 80 °C erwärmt und un-Alkyl sulfate, the sodium silicate and the alkyl glycoside, the zeolite in the form of an approximately 50% by weight aqueous slurry, the alkyl glycoside as an approximately 50% by weight aqueous solution and the sodium silicate in the form of an approximately 35% by weight water glass solution was set, an aqueous slurry containing 44 wt .-% water was generated from the raw materials listed in Table 1. This slurry, which had viscosities of 4500 mPa.s to 6400 mPa.s at 60 ° C to 80 ° C, was heated to temperatures of approximately 60 ° C to 80 ° C and
Tabelle 1: Pulverzusam ensetzunq fGew.-%1Table 1: Powder composition f% by weight 1
a) Ci2/i4-Alkylglucosid, Polymerisationsgrad 1,4 b) Lineares (Sulfopon(R) T, Hersteller Henkel) c) Verhältnis Siθ2 zu Na2θ : 3,0 d) Acrylsäure/Maleinsäure-Copolymer, Na-Salz (Sokalan(R) CP 5, Hersteller BASF) ter einem Druck von 40 bar in einem Trockenturm versprüht, wobei Heißluft (Temperatur 145 °C bis 160 °C im Ringkanal) im Gegenstrom geführt wurde. Dabei wurde das in Tabelle 1 durch seine Zusammensetzung charakterisierte rieselfähige Pulver Ml mit einer mittleren Korngröße um 0,5 mm erhalten, das frei von Teilchen über 1,8 mm Durchmesser war, Staubanteile von 0,15 Gew.-% aufwies und eine Schüttdichte von 540 Gramm pro Liter besaß. a) Ci2 / i4-alkyl glucoside, degree of polymerization 1.4 b) linear (Sulfopon ( R ) T, manufacturer Henkel) c) ratio SiO 2 to Na 2 O: 3.0 d) acrylic acid / maleic acid copolymer, Na salt (Sokalan ( R ) CP 5, manufacturer BASF) at a pressure of 40 bar in one Sprayed drying tower, whereby hot air (temperature 145 ° C to 160 ° C in the ring channel) was conducted in counterflow. The free-flowing powder Ml characterized in Table 1 by its composition was obtained with an average grain size of around 0.5 mm, which was free of particles over 1.8 mm in diameter, had dust contents of 0.15% by weight and a bulk density of Had 540 grams per liter.
Zum Vergleich wurde aus den gleichen Mengen der gleichen Rohstoffe wie bei Produkt Ml unter ansonsten gleichen Bedingungen ein Pulver hergestellt, welches nur die Hälfte der angegebenen Menge an Alkylglykosid aus der versprühten Aufschlämmung enthielt und dem die restliche Alkylglykosid- Menge durch Aufsprühen einer hochkonzentrierten wäßrigen Lösung dieses Inhaltsstoffes zugegeben wurde. Dieses Produkt wies trotz erhöhter Neigung zur Verklumpung auch deutlich höhere Staubanteile als Produkt Ml auf.For comparison, a powder was prepared from the same amounts of the same raw materials as for product Ml under otherwise identical conditions, which contained only half of the stated amount of alkyl glycoside from the sprayed slurry and which the remaining amount of alkyl glycoside by spraying a highly concentrated aqueous solution of this Ingredient was added. Despite the increased tendency to clump, this product also had significantly higher dust contents than product Ml.
Beispiel 2Example 2
Durch einfaches Vermischen der in der nachfolgenden Tabelle angegebenen Menge des erfindungsgemäßen Pulvers mit üblichen Waschmittelinhaltsstoffen wurde das Waschmittel Wl hergestellt. Dieses wies in Waschversuchen unter Anwendungsbedingungen (Trommelwaschmaschine Miele W 716, 3,5 kg normal verschmutzte Wäsche, Wasserhärte 16 °d, Dosierung 98 g Waschmittel) im Durchschnitt über alle Anschmutzungen sowohl bei 30 °C als auch bei 60 °C und 90 °C eine Waschkraft auf, die mindestens das Niveau eines zu Ver¬ gleichszwecken getesteten handelsüblichen Vollwaschmittels mit einer Fettalkylpolyethoxylat/Alkylbenzolsulfonat-Tensidkomponente erreichte. Vor allem bei Kosmetik-Anschmutzungen schnitt das erfindungsgemäße Mittel deutlich besser ab. The detergent W1 was prepared by simply mixing the amount of the powder according to the invention specified in the table below with conventional detergent ingredients. In washing tests under application conditions (drum washing machine Miele W 716, 3.5 kg of normally soiled laundry, water hardness 16 ° d, dosage 98 g detergent), this showed an average of all soiling at 30 ° C as well as at 60 ° C and 90 ° C a washing power which at least reached the level of a commercial heavy-duty detergent tested for comparison purposes with a fatty alkyl polyethoxylate / alkylbenzenesulfonate surfactant component. The agent according to the invention performed significantly better, especially in the case of cosmetic soiling.
Tabelle 2: WaschmittelZusammensetzung fGew.-%1Table 2: Detergent composition f% by weight 1
a) Monohydrat b) Tetraacetylethylendiamin-Granulat, hergestellt gemäß europäischer Pa¬ tentschrift EP 037026 c) Protease-Granulat (BLAP(R) 140, Hersteller Biozym) d) 10 Gew.-% Paraffin enthaltendes Schauminhibitor-Konzentrat, Rest Na- Sulfat, Na-Silikat und Na-Carboxymethylcellulose, hergestellt gemäß europäischer Patentanmeldung EP 309931 a) monohydrate b) tetraacetylethylenediamine granules, produced in accordance with European patent specification EP 037026 c) protease granules (BLAP ( R ) 140, manufacturer Biozym) d) foam inhibitor concentrate containing 10% by weight of paraffin, remainder Na sulfate, Na silicate and Na carboxymethyl cellulose, produced according to European patent application EP 309931

Claims

Patentansprüche Claims
1. Verfahren zur Herstellung pulverförmiger Tensidmischungen, enthaltend Alkylsulfat, Alkylglykosid und anorganisches Trägermaterial, durch Trocknen fließfähiger, wäßriger, tensidhaltiger Mischungen, dadurch gekennzeichnet, daß man eine Menge von 2 bis 15 Gewichtsteilen Alkyl¬ sulfat der Formel I,1. A process for the preparation of powdered surfactant mixtures containing alkyl sulfate, alkyl glycoside and inorganic carrier material by drying flowable, aqueous, surfactant-containing mixtures, characterized in that an amount of 2 to 15 parts by weight of alkyl sulfate of the formula I,
R!-0S03X (I)R! -0S03X (I)
in der R1 einen Alkylrest mit 10 bis 20 C-Atomen und X ein Alkali-, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituiertes Ammoniumion bedeuten, eine Menge von 1 bis 5 Gewichtsteilen Alkylgly¬ kosid der Formel II,in which R 1 is an alkyl radical having 10 to 20 C atoms and X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion, an amount of 1 to 5 parts by weight of alkyl glycoside of the formula II,
R2-0(G)n (II)R 2 -0 (G) n (II)
in der R2 einen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und n eine Zahl von 1 bis 10 bedeuten, wobei das GewichtsVerhältnis von Alkylsulfat zu Alkylglykosid 8:1 bis 1:1 beträgt, und eine Menge von 20 bis 100 Gewichtsteilen eines im wesentlichen anorganischen phosphatfreien Trägermaterials, welches Alkalicarbonat und Alkalialu- mosilikat im Gewichtsverhältnis 2:1 bis 1:3 enthält, mit so viel Was¬ ser mischt, daß eine bei Temperaturen unter 95 °C fließfähige und pumpbare Mischung mit einer Viskosität von 3000 mPa*s bis 15000 mPa'S, gemessen bei 60 °C bis 80 °C, entsteht, und dieser durch Sprühtrocknung unter Verwendung von Trocknungsgasen mit Temperaturen unter 250 °C das Wasser soweit entzieht, daß ein pulverförmiges, rie¬ selfähiges Produkt entsteht.in which R2 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10, the weight ratio of alkyl sulfate to alkyl glycoside being 8: 1 to 1: 1, and an amount of 20 to 100 parts by weight an essentially inorganic phosphate-free carrier material, which contains alkali carbonate and alkali alumino-silicate in a weight ratio of 2: 1 to 1: 3, with so much water that a mixture which is flowable and pumpable at temperatures below 95 ° C. and has a viscosity of 3000 mPa * s up to 15000 mPa'S, measured at 60 ° C to 80 ° C, and this removes the water by spray drying using drying gases at temperatures below 250 ° C to such an extent that a powdery, free-flowing product is formed.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man 3 bis 10 Gewichtsteile Alkylsulfat gemäß Formel I, 2 bis 3 Gewichtsteile Alkylglykosid gemäß Formel II und 25 bis 80 Gewichtsteile des anorga¬ nischen Trägermaterials mit so viel Wasser mischt, daß eine mindestens 35 Gew.- , insbesondere 40 Gew.-% bis 50 Gew.-% Wasser enthaltende Mischung entsteht.2. The method according to claim 1, characterized in that 3 to 10 parts by weight of alkyl sulfate according to formula I, 2 to 3 parts by weight of alkyl glycoside according to formula II and 25 to 80 parts by weight of the inorganic carrier material are mixed with so much water that at least one 35 wt .-%, in particular 40 wt .-% to 50 wt .-% water-containing mixture.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Ge¬ wichtsverhältnis von Alkylsulfat zu Alkylglykosid 5:1 bis 2:1 beträgt.3. The method according to claim 1 or 2, characterized in that the weight ratio of alkyl sulfate to alkyl glycoside is 5: 1 to 2: 1.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man Trocknungsgase mit Temperaturen von 120 °C bis 240 °C, insbe¬ sondere von 140 °C bis 210 °C einsetzt.4. The method according to any one of claims 1 to 3, characterized in that drying gases with temperatures of 120 ° C to 240 ° C, in particular from 140 ° C to 210 ° C are used.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das anorganische Trägermaterial 40 Gew.- bis 60 Gew.-% Alkali- alumosilikat, insbesondere Zeolith NaA und/oder NaX, 20 Gew.-% bis 40 Gew.-% Alkalicarbonat, bis zu 20 Gew.- weitere anorganische Salze und nicht mehr als 20 Gew.-% organisches Material, insbesondere Polycarboxylat, enthält.5. The method according to any one of claims 1 to 4, characterized in that the inorganic carrier material 40 wt .-% to 60 wt .-% alkali aluminosilicate, in particular zeolite NaA and / or NaX, 20 wt .-% to 40 wt .-% % Alkali carbonate, up to 20% by weight of further inorganic salts and not more than 20% by weight of organic material, in particular polycarboxylate.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das anorganische Trägermaterial zusätzlich zu Alkalialumosilikat und Alkalicarbonat 1 Gew.- bis 10 Gew.-%, jeweils bezogen auf gesam¬ tes Trägermaterial, Alkalihydrogencarbonat, Alkalichlorid oder Alka- lisilikat oder ein Gemisch aus diesen enthält, wobei das Trägermate¬ rial frei von Alkalisilikat mit einem Molverhältnis Siθ2 zu Alkalioxid bis zu 2 ist und der Anteil an Alkalisilikat mit einem Molverhältnis Siθ2 zu Alkalioxid über 2 nicht mehr als 5 Gew.-%, bezogen auf gesam¬ tes Trägermaterial, beträgt.6. The method according to any one of claims 1 to 5, characterized in that the inorganic carrier material in addition to alkali alumosilicate and alkali carbonate 1 wt .-% to 10 wt .-%, each based on the total carrier material, alkali metal bicarbonate, alkali metal chloride or alkali metal silicate or contains a mixture of these, the carrier material being free from alkali silicate with a molar ratio of SiO 2 to alkali oxide up to 2 and the proportion of alkali silicate with a molar ratio of SiO 2 to alkali oxide not exceeding 5% by weight, based on the total t carrier material.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das anorganische Trägermateria1 zusätzlich zu Alkalialumosilikat und Alkal carbonat 1 Gew.-% bis 15 Gew.-%, insbesondere 5 Gew.-% bis 13 Gew.-%, jeweils bezogen auf gesamtes Trägermaterial, wasserlös¬ liches Salz polymerer Polycarbonsäuren enthält, welche durch Polyme¬ risation von Acrylsäure-, Methacrylsäure- und/oder Maleinsäure- Monomeren beziehungsweise deren Salzen hergestellt werden können. 7. The method according to any one of claims 1 to 6, characterized in that the inorganic carrier material 1 in addition to alkali alumosilicate and alkali carbonate 1 wt .-% to 15 wt .-%, in particular 5 wt .-% to 13 wt .-%, each based on the entire carrier material, contains water-soluble salt of polymeric polycarboxylic acids which can be prepared by polymerizing acrylic acid, methacrylic acid and / or maleic acid monomers or their salts.
8. Pulverförmige, schütt- und rieselfähige Tensidmischung, die durch Sprühtrocknen unter Verwendung von Trocknungsgasen mit Temperaturen unter 250 °C einer gießfähigen wäßrigen Mischung ihrer Bestandteile erhalten wird, und die 10 bis 30 Gew.- Alkylsulfat der Formel I,8. Powdery, pourable and free-flowing surfactant mixture which is obtained by spray drying using drying gases at temperatures below 250 ° C. of a pourable aqueous mixture of its constituents, and the 10 to 30% by weight alkyl sulfate of the formula I,
Ri-OSOsX (I)Ri-OSOsX (I)
in der R* einen Alkylrest mit 10 bis 20 C-Atomen und X ein Alkali-, Ammonium- oder Alkyl- beziehungsweise Hydroxyalkyl-substituiertes Ammoniumion bedeuten, 2 bis 10 Gew.-% Alkylglykosid der Formel II,in which R * is an alkyl radical having 10 to 20 C atoms and X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion, 2 to 10% by weight of alkyl glycoside of the formula II,
R2-0(G)n (II)R 2 -0 (G) n (II)
in der R2 einen Alkylrest mit 8 bis 22 C-Atomen, G eine Glykoseeinheit und n eine Zahl von 1 bis 10 bedeuten, wobei das Gewichtsverhältnis von Alkylsulfat zu Alkylglykosid 8:1 bis 1:1 beträgt, 45 bis 70 Gew.-% eines im wesentlichen anorganischen Trägermaterials, welches Alkalicarbonat und Alkalialumosilikat im Gewichtsverhältnis 2:1 bis 1:3 enthält, nicht über 5 Gew.-% insbesondere 0,1 Gew.-% bis 3 Gew.-% weiteres Tensid, nicht über 1 Gew.-% insbesondere 0,01 Gew.-% bis 0,5 Gew.-% optischen Aufheller, nicht über 2 Gew.-% insbesondere 0,1 Gew.-% bis 1 Gew.-% Schauminhi¬ bitor, nicht über 3 Gew.-% insbesondere 0,5 Gew.-% bis 2 Gew.-% Vergrauungsinhibitor, nicht über 5 Gew.-% insbesondere 0,1 Gew.-% bis 2 Gew.-% Komplexbild¬ ner für Schwermetalle und bis zu 20 Gew.-% Wasser enthält.in which R 2 is an alkyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number from 1 to 10, the weight ratio of alkyl sulfate to alkyl glycoside being 8: 1 to 1: 1, 45 to 70% by weight an essentially inorganic carrier material which contains alkali carbonate and alkali alumosilicate in a weight ratio of 2: 1 to 1: 3, not more than 5% by weight, in particular 0.1% by weight to 3% by weight, of further surfactant, not more than 1% by weight. %, in particular 0.01% by weight to 0.5% by weight of optical brightener, not more than 2% by weight, in particular 0.1% by weight to 1% by weight of foam inhibitor, not more than 3% by weight % in particular 0.5% by weight to 2% by weight of graying inhibitor, not more than 5% by weight in particular 0.1% by weight to 2% by weight of complexing agent for heavy metals and up to 20% by weight .-% contains water.
9. Tensidmischung nach Anspruch 8, dadurch gekennzeichnet, daß sie 12 bis 25 Gew.-% Alkylsulfat gemäß Formel I, 3 bis 8 Gew.-% Alkylglykosid gemäß Formel II, 52 bis 65 Gew.-% Trägermaterial und 5 bis 15 Gew.-% Wasser enthält.9. surfactant mixture according to claim 8, characterized in that it contains 12 to 25 wt .-% alkyl sulfate according to formula I, 3 to 8 wt .-% alkyl glycoside according to formula II, contains 52 to 65% by weight of carrier material and 5 to 15% by weight of water.
10. Tensidmischung nach Anspruch 8 oder 9, dadurch gekennzeichnet, daß das Alkylsulfat der Formel I einen Alkylrest Rl mit 12 bis 18 C-Atomen besitzt.10. surfactant mixture according to claim 8 or 9, characterized in that the alkyl sulfate of formula I has an alkyl radical Rl having 12 to 18 carbon atoms.
11. Tensidmischung nach einem der Ansprüche 8 bis 10, dadurch gekenn¬ zeichnet, daß das Alkylglykosid der Formel II ein Alkylglucosid ist und einen Oligomerisierungsgrad n unter 1,5, insbesondere von 1,2 bis 1,4, besitzt.11. A surfactant mixture according to one of claims 8 to 10, characterized in that the alkyl glycoside of the formula II is an alkyl glucoside and has a degree of oligomerization n below 1.5, in particular from 1.2 to 1.4.
12. Verwendung einer pulverförmigen Tensidmischung gemäß einem der An¬ sprüche 8 bis 11 als schütt- und rieselfähiges Vorgemisch zur Her¬ stellung von partikelförmigen Wasch- oder Reinigungsmitteln.12. Use of a powdery surfactant mixture according to one of claims 8 to 11 as a pourable and pourable premix for the production of particulate detergents or cleaning agents.
13. Verwendung nach Anspruch 12, dadurch gekennzeichnet, daß das entste¬ hende Mittel13. Use according to claim 12, characterized in that the entste¬ existing agent
50 Gew.-% bis 80 Gew.-%, insbesondere 65 Gew.-% bis 75 Gew.-%50% by weight to 80% by weight, in particular 65% by weight to 75% by weight
Tensidmischung gemäß einem der Ansprüche 8 bis 11, bis zu 25 Gew.-%, insbesondere 12 Gew.-% bis 20 Gew.-% Bleichmittel, bis zu 10 Gew.-%, insbesondere 2 Gew.-% bis*8 Gew.-% Bleichaktivator, bis zu 1 Gew.-%, insbesondere 0,1 Gew.-% bis 1 Gew.-% Schauminhibitor, bis zu 2 Gew.-%, insbesondere 0,4 Gew.-% bis 1,2 Gew.-% Enzym, bis zu 50 Gew.-%, insbesondere 25 Gew.-% bis 35 Gew.-% Abrasivstoff, und bis zu 5 Gew.-%, insbesondere 0,5 Gew.-% bis 2 Gew.-% zusätzliches, insbesondere nichtionisches Tensid enthält. Surfactant mixture according to one of claims 8 to 11, up to 25% by weight, in particular 12% by weight to 20% by weight of bleach, up to 10% by weight, in particular 2% by weight to * 8% by weight. % Bleach activator, up to 1% by weight, in particular 0.1% by weight to 1% by weight of foam inhibitor, up to 2% by weight, in particular 0.4% by weight to 1.2% by weight. % Enzyme, up to 50% by weight, in particular 25% by weight to 35% by weight of abrasive material, and up to 5% by weight, in particular 0.5% by weight to 2% by weight, of additional , in particular contains nonionic surfactant.
EP92923773A 1991-11-30 1992-11-23 Powdery surface-active agent mixture Expired - Lifetime EP0614484B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4139551 1991-11-30
DE4139551A DE4139551A1 (en) 1991-11-30 1991-11-30 POWDERED SURFACE BLEND
PCT/EP1992/002694 WO1993011212A1 (en) 1991-11-30 1992-11-23 Powdery surface-active agent mixture

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EP0614484A1 true EP0614484A1 (en) 1994-09-14
EP0614484B1 EP0614484B1 (en) 1997-04-09

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DE19524464C2 (en) * 1995-07-10 2000-08-24 Cognis Deutschland Gmbh Process for the production of sugar surfactant granules
US5571446A (en) * 1995-07-27 1996-11-05 Diversey Corporation Anionic stabilized enzyme based clean-in-place system
DE19624637A1 (en) * 1996-06-21 1998-01-02 Henkel Kgaa Washing process for textiles with improved care properties
GB2318584A (en) * 1996-10-25 1998-04-29 Procter & Gamble Process for preparing detergent compositions by spray drying
DE19710153C1 (en) 1997-03-12 1998-02-12 Henkel Kgaa Neutral sugar surfactant granulation from e.g. alkyl oligo:glycoside
EP0879876A1 (en) * 1997-05-21 1998-11-25 The Procter & Gamble Company Process for preparation of granular detergent composition or component comprising a water-soluble cationic surfactant
DE10018812A1 (en) 2000-04-15 2001-10-25 Cognis Deutschland Gmbh Nonionic surfactant granulate, used in surfactant, cosmetic or pharmaceutical formulation or laundry or other detergent, is obtained by granulating and simultaneously drying aqueous surfactant paste in presence of organic polymeric carrier

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US4536319A (en) * 1983-10-04 1985-08-20 The Procter & Gamble Company Compositions comprising alkylpolysaccharide detergent surfactant
WO1990004630A1 (en) * 1988-10-21 1990-05-03 Henkel Corporation A process for preparing a detergent slurry and particulate detergent composition
DE4102745A1 (en) * 1991-01-30 1992-08-06 Henkel Kgaa POWDERED SURFACE BLEND

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See references of WO9311212A1 *

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ES2100367T3 (en) 1997-06-16
DE4139551A1 (en) 1993-06-03
ATE151452T1 (en) 1997-04-15
DE59208338D1 (en) 1997-05-15
JPH07501564A (en) 1995-02-16
WO1993011212A1 (en) 1993-06-10

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